Mixed Decyl Mercaptans Compositions and Methods of Making Same

ABSTRACT

Compositions comprising branched C 10  mercaptans selected from the group consisting of 5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane, 4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane, 5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane, 4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinations thereof. Compositions comprising C 11+  mercaptans, wherein the C 11+  mercaptans are characterized by structure R 6 —SH, wherein R 6  is an alkyl group derived from one or more C 11+  monoolefins, and wherein the one or more C 11+  monoolefins comprise C 11  internal monoolefins, C 12  internal monoolefins, C 13  internal monoolefins, C 14  internal monoolefins, 1-tetradecene, 1-hexadecene, or combinations thereof. Compositions comprising branched C 10+  mercaptans, wherein the branched C 10+  mercaptans are characterized by structure R 14 —SH, wherein R 14  is an alkyl group derived from one or more branched C 10  to C 30  monoolefins.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S. patentapplication Ser. No. 15/669,097 filed Aug. 4, 2017, which is acontinuation-in-part application of U.S. patent application Ser. No.15/632,910 filed Jun. 26, 2017, published as U.S. Patent ApplicationPublication No. U.S. 2017/0291872 A1, which is a continuation of andclaims priority to U.S. patent application Ser. No. 15/296,837 filedOct. 18, 2016, now U.S. Pat. No. 9,738,601, which is a divisional of andclaims priority to U.S. patent application Ser. No. 14/981,469 filedDec. 28, 2015, now U.S. Pat. No. 9,512,071, and entitled “Mixed DecylMercaptans Compositions and Methods of Making Same,” each of which isincorporated by reference herein in its entirety.

U.S. patent application Ser. No. 15/669,097 is also acontinuation-in-part application of U.S. patent application Ser. No.15/463,867 filed Mar. 20, 2017, published as U.S. Patent ApplicationPublication No. US 2017/0190811 A1, which is a continuation of andclaims priority to U.S. patent application Ser. No. 15/284,802 filedOct. 4, 2016, now U.S. Pat. No. 9,631,039, which is a divisional of andclaims priority to U.S. patent application Ser. No. 14/981,428 filedDec. 28, 2015, now U.S. Pat. No. 9,512,248, and entitled “Mixed DecylMercaptans Compositions and Use Thereof as Chain Transfer Agents,” eachof which is incorporated by reference herein in its entirety.

This application is related to U.S. patent application Ser. No.15/284,809 filed Oct. 4, 2016, now U.S. Pat. No. 9,527,090, which is adivisional of and claims priority to U.S. patent application Ser. No.14/981,475 filed Dec. 28, 2015, now U.S. Pat. No. 9,505,011, andentitled “Mixed Decyl Mercaptans Compositions and Use Thereof as MiningChemical Collectors,” each of which is incorporated by reference hereinin its entirety.

TECHNICAL FIELD

The present disclosure relates to compositions containing C₁₀₊mercaptans and/or sulfides (C₂₀₊) and methods of making same. Morespecifically, the present disclosure relates to compositions containingmixed C₁₀₊ mercaptans and/or mixed C₂₀₊ sulfides, and methods of makingsame.

BACKGROUND

Mercaptans, which are also known as thiols, are organic compounds usedin diverse applications. Some mercaptans can be used as precursors foragriculture chemicals or as natural gas additives. While processes formaking mercaptans are available, preparing individual mercaptans can becostly due numerous purification steps required for the feedstock and/ormercaptan product. However, many applications may not require a singlepure mercaptan compound, but could utilize mercaptan mixtures. Thus,there is a need to develop mercaptan compositions suitable for suchapplications, and methods of making same.

BRIEF SUMMARY

Disclosed herein is a composition comprising mercaptans, wherein atleast about 50 wt. % of the mercaptans are branched C₁₀ mercaptansselected from the group consisting of 5-methyl-1-mercapto-nonane(represented by Structure A), 3-propyl-1-mercapto-heptane (representedby Structure B), 4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

Also disclosed herein is a composition comprising sulfides, wherein atleast about 50 wt. % of the sulfides are branched C₂₀ sulfidesrepresented by the structure R¹—S—R², wherein R¹ and R² are eachindependently a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

Further disclosed herein is a composition comprising (A) at least about25 wt. % C₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof, and (B) at least about 5 wt. % C₂₀ sulfidesrepresented by the structure R¹—S—R², wherein R¹ and R² are eachindependently a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

Further disclosed herein is a composition comprising (A) from at leastabout 50 wt. % to at least about 90 wt. % mercaptans, wherein at leastabout 50 wt. % of the mercaptans are branched C₁₀ mercaptans selectedfrom the group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof, and (B) from at least about 10 wt. % to at leastabout 30 wt. % sulfides, wherein at least 50 wt. % of the sulfides arebranched C₂₀ sulfides represented by the structure R¹—S—R², wherein R¹and R² are each independently a functional group derived from an olefinselected from the group consisting of 5-methyl-1-nonene (represented byStructure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), and combinations thereof.

Further disclosed herein is a composition comprising (A) at least about25 wt. % C₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof, (B) at least about 5 wt. % C₂₀ sulfidesrepresented by the structure R¹—S—R², wherein R¹ and R² are eachindependently a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof, and one or more of the following components(C)-(I), (C) less than about 5 wt. % C₈ mercaptans, (D) less than about15 wt. % C₁₂ mercaptans, (E) less than about 15 wt. % C₁₄ mercaptans,(F) less than about 5 wt. % C₁₆ mercaptans and/or C₁₈ mercaptans, (G)less than about 1 wt. % C₁₆₋₃₆ sulfides represented by the structureR³—S—R⁴, wherein R³ and R⁴ are each independently a functional groupderived from an olefin selected from the group consisting of C₈monoolefins, C₁₀ monoolefins, C₁₂ monoolefins, C₁₄ monoolefins, C₁₆monoolefins, and C₁₈ monoolefins, wherein R³ and R⁴ are not bothbranched C₁₀ monoolefins, (H) less than about 10 wt. % unreacted C₈₋₁₈monoolefins, and (I) less than about 10 wt. % non-olefin impuritiesselected from the group consisting of C₈₋₁₄ alkanes, cyclohexane,methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene,xylene, mesitylene, hexamethylbenzene, C₄₋₁₂ alcohols,2-ethyl-1-hexanol, and 2-ethylhexyl-2-ethylhexanoate.

Further disclosed herein is a process comprising reacting hydrogensulfide (H₂S) and a feedstock comprising one or more branched C₁₀monoolefins in the presence of an initiating agent to produce a crudecomposition, wherein the branched C₁₀ monoolefins comprise5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

Further disclosed herein is a process comprising reacting hydrogensulfide (H₂S) and a feedstock comprising one or more C₁₁₊ monoolefins inthe presence of an initiating agent to produce a C₁₁₊ mercaptans crudecomposition, wherein the feedstock comprises at least about 70 wt. % ofone or more C₁₁₊ monoolefins, based on the total weight of thefeedstock, and wherein the C₁₁₊ monoolefins comprise C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; C₁₄ and C₁₆linear alpha monoolefins; or combinations thereof.

Further disclosed herein is a process comprising reacting hydrogensulfide (H₂S) and a feedstock comprising one or more C₁₁₊ monoolefins inthe presence of an initiating agent to produce a C₁₁₊ mercaptans crudecomposition, wherein the feedstock comprises at least about 70 wt. % ofone or more C₁₁₊ monoolefins, based on the total weight of thefeedstock, and wherein the C₁₁₊ monoolefins comprise C₁₁ internalmonoolefins, C₁₂ internal monoolefins, C₁₃ internal monoolefins, C₁₄internal monoolefins, 1-tetradecene, 1-hexadecene, or combinationsthereof, and recovering a reaction product from the C₁₁₊ mercaptanscrude composition, wherein the reaction product comprises (A) at leastabout 50 wt. % C₁₁₊ mercaptans, based on the total weight of thereaction product, wherein the C₁₁₊ mercaptans are characterized bystructure R⁶—SH, wherein R⁶ is an alkyl group derived from the one ormore C₁₁₊ monoolefins; and (B) less than about 20 wt. %, C₂₂₊ sulfides,based on the total weight of the reaction product, wherein the C₂₂₊sulfides are characterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸are each independently an alkyl group derived from the one or more C₁₁₊monoolefins.

Further disclosed herein is a composition comprising C₁₀₊ mercaptans,wherein at least about 50 wt. % of the C₁₀₊ mercaptans are branched C₁₀to C₃₀ mercaptans characterized by the general formula R¹⁴—SH, whereinR¹⁴ is a branched alkyl group; and wherein R¹⁴ has from 10 to 30 carbonatoms.

Further disclosed herein is a composition comprising C₂₀₊ sulfides,wherein at least about 50 wt. % of the C₂₀₊ sulfides are branched C₂₀ toC₆₀ sulfides represented by structure R¹⁰—S—R¹¹, wherein R¹⁰ and R¹¹ areeach independently a functional group derived from an olefin, andwherein the olefin comprises a branched C₁₀ to C₃₀ monoolefin.

Further disclosed herein is a composition comprising (A) at least about25 wt. % branched C₁₀ to C₃₀ mercaptans characterized by the generalformula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group; and wherein R¹⁴has from 10 to 30 carbon atoms, and (B) at least about 5 wt. % branchedC₂₀ to C₆₀ sulfides represented by structure R¹⁰—S—R¹¹, wherein R¹⁰ andR¹¹ are each independently a functional group derived from an olefin,and wherein the olefin comprises a branched C₁₀ to C₃₀ monoolefin.

Further disclosed herein is a process comprising reacting hydrogensulfide (H₂S) and a feedstock comprising one or more branched C₁₀ to C₃₀monoolefins in the presence of an initiating agent to produce a branchedC₁₀₊ mercaptans crude composition, wherein the branched C₁₀₊ mercaptanscrude composition comprises branched C₁₀ to C₃₀ mercaptans characterizedby the general formula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group;and wherein R¹⁴ has from 10 to 30 carbon atoms.

BRIEF DESCRIPTION OF THE DRAWINGS

For a detailed description of the preferred embodiments of the disclosedcompositions and methods of making same, reference will now be made tothe accompanying drawings in which:

FIG. 1 displays a reaction schematic for addition of hydrogen sulfide(H₂S) to an olefin;

FIG. 2 displays a GC trace of a crude product from an UV initiatedreaction after removal of residual H₂S;

FIG. 3 displays a GC trace of a reaction product from an UV initiatedreaction after removal of lights;

FIG. 4 displays a GC trace of a crude product from an UV initiatedreaction after removal of residual H₂S;

FIG. 5 displays a GC trace of a reaction product from an UV initiatedreaction after removal of lights;

FIG. 6 displays a comparison of GC traces for a product obtained by UVinitiation and a product obtained by acid catalysis. The upperchromatogram is the UV-initiated C₁₀ mercaptan product, and the lowerchromatogram is the acid catalyzed C₁₀ mercaptan product;

FIG. 7 displays a comparison of GC traces for a C₁₀ mercaptan fractionisolated from a product obtained by UV initiation and a C₁₀ mercaptanfraction isolated from a product obtained by acid catalysis, andparticularly, representative GC profiles of the purified C₁₀ mercaptanreaction product. The upper chromatogram is the acid catalyzed C₁₀mercaptan product, and the lower chromatogram is the UV-initiated C₁₀mercaptan product; and

FIG. 8 displays a GC trace of a crude product from a reaction catalyzedby a hydrodesulfurization catalyst after removal of residual H₂S.

DETAILED DESCRIPTION

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure, butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Groups of elements of the Periodic Table are indicated using thenumbering scheme indicated in the version of the Periodic Table ofelements published in Chemical and Engineering News, 63(5), 27, 1985. Insome instances, a group of elements can be indicated using a common nameassigned to the group; for example, alkali metals for Group 1 elements,alkaline earth metals (or alkaline metals) for Group 2 elements,transition metals for Groups 3-12 elements, and halogens for Group 17elements.

Regarding claim transitional terms or phrases, the transitional term“comprising”, which is synonymous with “including,” “containing,”“having,” or “characterized by,” is inclusive or open-ended and does notexclude additional, unrecited elements or method steps. The transitionalphrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The transitional phrase “consisting of” limitsthe scope of a claim to the specified materials or steps and those thatdo not materially affect the basic and novel characteristic(s) of theclaimed invention. The term “consisting essentially of” occupies amiddle ground between closed terms like “consisting of” and fully openterms like “comprising.” Absent an indication to the contrary, whendescribing a compound or composition, “consisting essentially of” is notto be construed as “comprising,” but is intended to describe the recitedcomponent that includes materials which do not significantly alter thecomposition or method to which the term is applied. For example, afeedstock consisting essentially of a material A can include impuritiestypically present in a commercially produced or commercially availablesample of the recited compound or composition. When a claim includesdifferent features and/or feature classes (for example, a method step,feedstock features, and/or product features, among other possibilities),the transitional terms comprising, consisting essentially of, andconsisting of apply only to the feature class to which is utilized andit is possible to have different transitional terms or phrases utilizedwith different features within a claim. For example, a method cancomprise several recited steps (and other non-recited steps), bututilize a catalyst system preparation consisting of specific steps, oralternatively, consisting essentially of specific steps, but utilize acatalyst system comprising recited components and other non-recitedcomponents.

While compositions and methods are described in terms of “comprising”(or other broad term) various components and/or steps, the compositionsand methods can also be described using narrower terms, such as “consistessentially of” or “consist of” the various components and/or steps.

The terms “a,” “an,” and “the” are intended, unless specificallyindicated otherwise, to include plural alternatives, e.g., at least one.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers, unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers, whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. By way of example, an “alkyl group” can formally be derivedby removing one hydrogen atom from an alkane, while an “alkylene group”can formally be derived by removing two hydrogen atoms from an alkane.Moreover, a more general term can be used to encompass a variety ofgroups that formally are derived by removing any number (“one or more”)of hydrogen atoms from a parent compound, which in this example can bedescribed as an “alkane group,” and which encompasses an “alkyl group,”an “alkylene group,” and materials having three or more hydrogens atoms,as necessary for the situation, removed from the alkane. Throughout, thedisclosure of a substituent, ligand, or other chemical moiety that canconstitute a particular “group” implies that the well-known rules ofchemical structure and bonding are followed when that group is employedas described. When describing a group as being “derived by,” “derivedfrom,” “formed by,” or “formed from,” such terms are used in a formalsense and are not intended to reflect any specific synthetic methods orprocedures, unless specified otherwise or the context requiresotherwise.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon.Non-limiting examples of hydrocarbyl groups include ethyl, phenyl,tolyl, propenyl, and the like. Similarly, a “hydrocarbylene group”refers to a group formed by removing two hydrogen atoms from ahydrocarbon, either two hydrogen atoms from one carbon atom or onehydrogen atom from each of two different carbon atoms. Therefore, inaccordance with the terminology used herein, a “hydrocarbon group”refers to a generalized group formed by removing one or more hydrogenatoms (as necessary for the particular group) from a hydrocarbon. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” canbe acyclic or cyclic groups, and/or can be linear or branched. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” caninclude rings, ring systems, aromatic rings, and aromatic ring systems,which contain only carbon and hydrogen. “Hydrocarbyl groups,”“hydrocarbylene groups,” and “hydrocarbon groups” include, by way ofexample, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl,cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups,among other groups, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.,halogenated alkane indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the alkane). Theterm “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or can be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl group are derived by removal of a hydrogen atom from a primary,secondary, and tertiary carbon atom, respectively, of an alkane. Then-alkyl group can be derived by removal of a hydrogen atom from aterminal carbon atom of a linear alkane.

An aliphatic compound is an acyclic or cyclic, saturated or unsaturatedcarbon compound, excluding aromatic compounds. Thus, an aliphaticcompound is an acyclic or cyclic, saturated or unsaturated carboncompound, excluding aromatic compounds; that is, an aliphatic compoundis a non-aromatic organic compound. An “aliphatic group” is ageneralized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from a carbon atom of an aliphaticcompound. Thus, an aliphatic compound is an acyclic or cyclic, saturatedor unsaturated carbon compound, excluding aromatic compounds. That is,an aliphatic compound is a non-aromatic organic compound. Aliphaticcompounds and therefore aliphatic groups can contain organic functionalgroup(s) and/or atom(s) other than carbon and hydrogen.

The term “substituted” when used to describe a compound or group, forexample, when referring to a substituted analog of a particular compoundor group, is intended to describe any non-hydrogen moiety that formallyreplaces a hydrogen in that group, and is intended to be non-limiting. Agroup or groups can also be referred to herein as “unsubstituted” or byequivalent terms, such as “non-substituted,” which refers to theoriginal group in which a non-hydrogen moiety does not replace ahydrogen within that group. “Substituted” is intended to be non-limitingand include inorganic substituents or organic substituents.

The term “olefin” whenever used in this specification and claims refersto hydrocarbons that have at least one carbon-carbon double bond that isnot part of an aromatic ring or an aromatic ring system. The term“olefin” includes aliphatic and aromatic, cyclic and acyclic, and/orlinear and branched hydrocarbons having at least one carbon-carbondouble bond that is not part of an aromatic ring or ring system unlessspecifically stated otherwise. Olefins having only one, only two, onlythree, etc., carbon-carbon double bonds can be identified by use of theterm “mono,” “di,” “tri,” etc., within the name of the olefin. Theolefins can be further identified by the position of the carbon-carbondouble bond(s).

The term “alkene” whenever used in this specification and claims refersto a linear or branched aliphatic hydrocarbon olefin that has one ormore carbon-carbon double bonds. Alkenes having only one, only two, onlythree, etc., such multiple bonds can be identified by use of the term“mono,” “di,” “tri,” etc., within the name. For example, alkamonoenes,alkadienes, and alkatrienes refer to linear or branched acyclichydrocarbon olefins having only one carbon-carbon double bond (acyclichaving a general formula of C_(n)H_(2n)), only two carbon-carbon doublebonds (acyclic having a general formula of C_(n)H_(2n-2)), and onlythree carbon-carbon double bonds (acyclic having a general formula ofC_(n)H_(2n-4)), respectively. Alkenes can be further identified by theposition of the carbon-carbon double bond(s). Other identifiers can beutilized to indicate the presence or absence of particular groups withinan alkene. For example, a haloalkene refers to an alkene having one ormore hydrogen atoms replaced with a halogen atom.

The term “alpha olefin” as used in this specification and claims refersto an olefin that has a carbon-carbon double bond between the first andsecond carbon atoms of the longest contiguous chain of carbon atoms. Theterm “alpha olefin” includes linear and branched alpha olefins unlessexpressly stated otherwise. In the case of branched alpha olefins, abranch can be at the 2 position (a vinylidene) and/or the 3 position orhigher with respect to the olefin double bond. The term “vinylidene”whenever used in this specification and claims refers to an alpha olefinhaving a branch at the 2 position with respect to the olefin doublebond. By itself, the term “alpha olefin” does not indicate the presenceor absence of other carbon-carbon double bonds unless explicitlyindicated.

The term “normal alpha olefin” whenever used in this specification andclaims refers to a linear aliphatic mono-olefin having a carbon-carbondouble bond between the first and second carbon atoms. It is noted that“normal alpha olefin” is not synonymous with “linear alpha olefin” asthe term “linear alpha olefin” can include linear olefinic compoundshaving a double bond between the first and second carbon atoms.

The terms “lights,” “light fraction,” or “light compounds” whenever usedin this specification and claims refers to compounds present in thereaction product with equal to or less than about 9 carbon atoms (C⁹⁻)per molecule. Nonlimiting examples of C⁹⁻ compounds that can be in thereaction product include C⁹⁻ monoolefins (e.g., unreacted C⁹⁻monoolefins), C⁹⁻ mercaptans, C⁹⁻ alkanes, C⁹⁻ alcohols, cyclohexane,methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene,xylene, mesitylene, 2-ethyl-1-hexanol, and the like, or combinationsthereof. Unless otherwise specifically indicated herein, the terms“lights,” “light fraction,” or “light compounds” whenever used in thisspecification and claims excludes hydrogen sulfide, as H₂S is typicallysubstantially consumed during the preceding reaction and/or removed fromthe reaction product (as discussed in more detail herein) prior tofurther processing of the reaction product (e.g., distillation thereof).For example, H₂S can be removed from the reaction product viadistillation, stripping, flashing, or other suitable means known tothose of skill in the art without removing any substantial amounts ofthe “lights,” “light fraction,” or “light compounds” from the reactionproduct. Not wanting to be limited by theory, this definition of“lights,” “light fraction,” or “light compounds” includes any compoundswith about nine or less carbon atoms present in the reaction productthat can be detected, even in trace amounts. As is known to one of skillin the art, the light fraction can also contain trace amounts of lowercarbon number sulfides.

The terms “intermediates” or “intermediate fraction” whenever used inthis specification and claims typically refers to compounds with aboutten to seventeen carbon atoms (C₁₀₋₁₇) per molecule. Nonlimitingexamples of C₁₀₋₁₇ compounds include C₁₀ mercaptans (including bothbranched and non-branched C₁₀ mercaptans), C₁₂₋₁₇ mercaptan isomers,C₁₂-C₁₇ sulfides, and the like, or combinations thereof. Not wanting tobe limited by theory, this definition of “intermediates” or“intermediate fraction” includes any compounds with about ten toseventeen carbon atoms present in the reaction product that can bedetected, even in trace amounts. As is known to one skilled in the art,the intermediate fraction can also contain trace amounts of lower carbonnumber compounds, including sulfides. In some embodiments (e.g., in theExamples described herein), a product can be recovered from theintermediate fraction (e.g., a C₁₀ mercaptan fraction), and theremaining C₁₁ to C₁₇ compounds (e.g., C₁₂₋₁₆ mercaptans) can be referredto as the intermediate fraction.

The terms “heavies” or “heavy fraction” whenever used in thisspecification and claims refers to compounds with about eighteen or morecarbon atoms (C₁₈₊) per molecule. Nonlimiting examples of C₁₈₊ productsinclude C₁₈ sulfides, C₂₀ sulfides, C₂₄ sulfides, C₂₈ sulfides, C₃₂sulfides, C₁₈ mercaptans, and the like, or combinations thereof. As isknown to those of skill in the art, the heavy fraction can also containtrace amounts of lower carbon number compounds, including mercaptans andsulfides.

These light, intermediate, and heavy fractions can be referred to as“rough-cuts,” in that they contain a plurality of compounds spreadacross a range of carbon atoms, i.e., a plurality of compounds having adifferent number of carbon atoms (e.g., a rough cut comprising C₁₀, C₁₁,C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, etc. compounds). These rough cuts are incontrast to one or more “fine-cuts” that contain a fewer number ofcompounds than the rough-cuts, for example, a C₁₀ fine cut (e.g., a C₁₀mercaptan fraction) derived from or otherwise recovered separately fromthe rough cut. Accordingly, a rough cut can be comprised of a number offine cuts, for example where a plurality of cuts are taken viadistillation over a period of time and across a ramped temperaturerange, and referred to collectively as a rough cut or individually asfine cuts. Those of ordinary skill in the art can produce a fine-cutfraction from a rough-cut fraction, for example via further distillation(e.g., a C₁₀ splitter, a C₂₀ splitter, etc.) or other purificationtechnique.

The terms “room temperature” or “ambient temperature” are used herein todescribe any temperature from 15° C. to 35° C. wherein no external heator cooling source is directly applied to the reaction vessel.Accordingly, the terms “room temperature” and “ambient temperature”encompass the individual temperatures and any and all ranges, subranges,and combinations of subranges of temperatures from 15° C. to 35° C.wherein no external heating or cooling source is directly applied to thereaction vessel. The term “atmospheric pressure” is used herein todescribe an earth air pressure wherein no external pressure modifyingmeans is utilized. Generally, unless practiced at extreme earthaltitudes, “atmospheric pressure” is about 1 atmosphere (alternatively,about 14.7 psi or about 101 kPa).

Features within this disclosure that are provided as a minimum value canbe alternatively stated as “at least” or “greater than or equal to” anyrecited minimum value for the feature disclosed herein. Features withinthis disclosure that are provided as a maximum value can bealternatively stated as “less than or equal to” or “below” any recitedmaximum value for the feature disclosed herein.

Within this disclosure, the normal rules of organic nomenclature willprevail. For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is (are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4 position and hydrogens located at the 2, 3,5, and 6 positions. By way of another example, reference to a3-substituted naphth-2-yl indicates that there is a non-hydrogensubstituent located at the 3 position and hydrogens located at the 1, 4,5, 6, 7, and 8 positions. References to compounds or groups havingsubstitutions at positions in addition to the indicated position will bereferenced using comprising or some other alternative language. Forexample, a reference to a phenyl group comprising a substituent at the 4position refers to a phenyl group having a non-hydrogen substituentgroup at the 4 position and hydrogen or any non-hydrogen group at the 2,3, 5, and 6 positions.

Use of the term “optionally” with respect to any element of a claim isintended to mean that the subject element is required, or alternatively,is not required. Both alternatives are intended to be within the scopeof the claim.

Unless otherwise specified, any carbon-containing group for which thenumber of carbon atoms is not specified can have, according to properchemical practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbonatoms, or any range or combination of ranges between these values. Forexample, unless otherwise specified, any carbon-containing group canhave from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20carbon atoms, from 1 to 15 carbon atoms, from 1 to 10 carbon atoms, orfrom 1 to 5 carbon atoms. Moreover, other identifiers or qualifyingterms can be utilized to indicate the presence or absence of aparticular substituent, a particular regiochemistry and/orstereochemistry, or the presence or absence of a branched underlyingstructure or backbone.

Processes and/or methods described herein utilize steps, features, andcompounds which are independently described herein. The process andmethods described herein may or may not utilize step identifiers (e.g.,1), 2), etc., a), b), etc., or i), ii), etc.), features (e.g., 1), 2),etc., a), b), etc., or i), ii), etc.), and/or compound identifiers(e.g., first, second, etc.). However, it should be noted that processesand/or methods described herein can have multiple steps, features (e.g.,reagent ratios, formation conditions, among other considerations),and/or multiple compounds having the same general descriptor.Consequently, it should be noted that the processes and/or methodsdescribed herein can be modified to use an appropriate step or featureidentifier (e.g., 1), 2), etc., a), b), etc., or i), ii), etc.) and/orcompound identifier (e.g., first, second, etc.) regardless of step,feature, and/or compound identifier utilized in a particular aspectand/or embodiment described herein and that step or feature identifierscan be added and/or modified to indicate individual differentsteps/features/compounds utilized within the process and/or methodswithout detracting from the general disclosure.

Embodiments disclosed herein can provide the materials listed assuitable for satisfying a particular feature of the embodiment delimitedby the term “or.” For example, a particular feature of the disclosedsubject matter can be disclosed as follows: Feature X can be A, B, or C.It is also contemplated that for each feature the statement can also bephrased as a listing of alternatives such that the statement “Feature Xis A, alternatively B, or alternatively C” is also an embodiment of thepresent disclosure whether or not the statement is explicitly recited.

The weight percent compositional aspects of the various compositionsdescribed herein (e.g., the weight percent of one or more compoundspresent in a composition) can be determined by gas chromatography (GC),gas chromatography-mass spectroscopy (GC-MS), Raman spectroscopy,nuclear magnetic resonance (NMR) spectroscopy, or any other suitableanalytical method known to those of skill in the art. For example,unless otherwise indicated, the weight percent compositional aspects ofthe various compositions described herein (e.g., the weight percent ofthe various sulfur-containing compounds such as C₁₀ mercaptans and C₂₀sulfides present in the compositions such as the crude, light fraction,intermediate fraction, heavy faction, etc.) can be determined using agas chromatograph with a flame ionization detector (GC-FID) detectorbased on the total GC peak areas (as described herein) and reported asgas chromatography (GC) area percent (GC area %), which is a commonanalytical technique for compositions comprising sulfur-containingcompounds. While not wishing to be bound by this theory, it is believedthat the amount in area % is very similar to the amount in weightpercent (wt. %), and these respective amounts need not be exactlyequivalent or interchangeable in order to be understood by a person ofordinary skill.

In an embodiment, a process of the present disclosure comprisesreacting, in a reactor, hydrogen sulfide (H₂S) and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of aninitiating agent to produce a crude composition (also referred to as acrude product); wherein the branched C₁₀ monoolefins comprise5-methyl-1-nonene, 3-propyl-1-heptene, 4-ethyl-1-octene,2-butyl-1-hexene, or combinations thereof; and wherein the crudecomposition comprises branched C₁₀ mercaptans and branched C₂₀ sulfides.

The crude composition can be further processed, for example viadistillation, to yield one or more products (also referred to asdistilled, purified, refined, finished, or final products) selected fromthe group consisting of mercaptan compositions (e.g., a compositioncomprising one or more branched C₁₀ mercaptans), sulfide compositions(e.g., a composition comprising one or more branched C₂₀ sulfides); andcompositions having both mercaptans (e.g., branched C₁₀ mercaptans) andsulfides (e.g., branched C₂₀ sulfides), referred to as mercaptan/sulfidecompositions.

In an embodiment, a mercaptan composition comprises branched C₁₀mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane,4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane,5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane,4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinationsthereof.

In an embodiment, a sulfide composition comprises branched C₂₀ sulfidesrepresented by the structure R¹—S—R², wherein R¹ and R² are eachindependently a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene, 3-propyl-1-heptene,4-ethyl-1-octene, 2-butyl-1-hexene, or combinations thereof.

In an embodiment, a mercaptan/sulfide composition comprises (A) branchedC₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane,4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane,5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane,4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinationsthereof; and (B) branched C₂₀ sulfides represented by the structureR¹—S—R², wherein R¹ and R² are each independently a functional groupderived from an olefin, wherein the olefin comprises 5-methyl-1-nonene,3-propyl-1-heptene, 4-ethyl-1-octene, 2-butyl-1-hexene, or combinationsthereof.

The mercaptan compositions, sulfide compositions, and mercaptan/sulfidecompositions can be salable or otherwise used for a variety of end usessuch as mining ore collector compositions and chain transfer agents.

In an embodiment, the compositions disclosed herein can be prepared by aprocess comprising reacting, in a reactor, hydrogen sulfide (H₂S) and afeedstock comprising one or more branched C₁₀ monoolefins in thepresence of an initiating agent to produce a crude (reaction product)composition, wherein the branched C₁₀ monoolefins comprise5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

Any feedstock comprising one or more branched C₁₀ monoolefins of thetype described herein can be used, for example a feedstock obtained froma commercial petroleum refining or petrochemical process. Suchfeedstocks can comprise other olefins in addition to the one or morebranched C₁₀ monoolefins of the type described herein, for examplelinear C₁₀ monoolefins as well as olefins having more or less than 10carbon atoms. In an embodiment, the feedstock comprises one or morebranched C₁₀ monoolefins and is obtained from a 1-hexene productionprocess effluent stream. In various embodiments, a feedstock obtainedfrom a 1-hexene production process effluent stream can comprise C₁₀monoolefins (e.g., branched and/or linear C₁₀ monoolefins) as well asolefins having more or less than 10 carbon atoms.

In an embodiment, the feedstock can comprise (a) at least about 76 mol%, alternatively at least about 78 mol %, alternatively at least about80 mol %, or alternatively at least about 82 mol % C₁₀ monoolefins, and(b) at least about 1 mol %, alternatively at least about 2 mol %,alternatively at least about 3 mol %, or alternatively at least about 4mol % C₁₄ monoolefins. In an embodiment, the feedstock can comprise (a)from about 76 mol % to about 92 mol %, alternatively from about 78 mol %to about 90 mol %, alternatively from about 80 mol % to about 88 mol %,or alternatively from about 82 mol % to about 86 mol % C₁₀ monoolefins;and (b) from about 1 mol % to about 12 mol %, alternatively from about 2mol % to about 10 mol %, alternatively from about 3 mol % to about 8 mol%, or alternatively from about 4 mol % to about 7 mol % C₁₄ monoolefins.For purposes of the disclosure herein, a feedstock comprising (a) atleast about 76 mol % C₁₀ monoolefins, and (b) at least about 1 mol % C₁₄monoolefins can also be referred to as a “first feedstock.” In anembodiment, the first feedstock is obtained from a 1-hexene productionprocess effluent stream, for example an effluent stream obtained from a1-hexene production process of the type disclosed in co-pendingInternational Patent Application PCT/US2015/40433, which is incorporatedby reference herein in its entirety.

In another embodiment, the feedstock can comprise at least about 95 mol%, alternatively at least about 96 mol %, alternatively at least about97 mol %, alternatively at least about 98 mol %, or alternatively atleast about 99 mol % C₁₀ monoolefins. For purposes of the disclosureherein, a feedstock comprising at least about 95 mol % C₁₀ monoolefinscan also be referred to as a “second feedstock.” In an embodiment, thesecond feedstock can be produced by purifying the first feedstock, suchas for example by distillation of an effluent stream obtained from a1-hexene production process of the type disclosed in co-pendingInternational Patent Application PCT/US2015/40433, which is incorporatedby reference herein in its entirety.

In an embodiment, the C₁₀ monoolefins of any feedstock described herein(e.g., a first feedstock or a second feedstock) can comprise, canconsist essentially of, or can be, 2-butyl-1-hexene, 3-propyl-1-heptene,4-ethyl-1-octene, and 5-methyl-1-nonene. In an embodiment, the C₁₀monoolefins of any feedstock described herein can comprise i) at leastabout 3 mol %, alternatively at least about 4 mol %, alternatively atleast about 5 mol %, alternatively at least about 6 mol %, alternativelyat least about 7 mol %, or alternatively at least about 8 mol %2-butyl-1-hexene (represented by Structure L), ii) at least about 8 mol%, alternatively at least about 9 mol %, alternatively at least about 10mol %, alternatively at least about 11 mol %, alternatively at leastabout 12 mol %, or alternatively at least about 13 mol %3-propyl-1-heptene (represented by Structure J), iii) at least about 6mol %, alternatively at least about 7 mol %, alternatively at leastabout 8 mol %, alternatively at least about 9 mol %, alternatively atleast about 10 mol %, or alternatively at least about 11 mol %4-ethyl-1-octene (represented by Structure K), and iv) at least about 20mol %, alternatively at least about 22 mol %, alternatively at leastabout 24 mol %, alternatively at least about 26 mol %, alternatively atleast about 28 mol %, or alternatively at least about 30 mol %5-methyl-1-nonene (represented by Structure I).

In an embodiment, the C₁₀ monoolefins of any feedstock described herein(e.g., a first feedstock or a second feedstock) can have a molar ratioof 2-butyl-1-hexene to 5-methyl-1-nonene of at least about 2:1,alternatively at least about 2.4:1, alternatively at least about 2.6:1,or alternatively at least about 2.8:1. In an embodiment, the C₁₀monoolefins of any feedstock described herein can have a molar ratio of3-propyl-1-heptene to 5-methyl-1-nonene of at least about 1.2:1,alternatively at least about 1.4:1, alternatively at least about 1.6:1,or alternatively at least about 1.8:1. In an embodiment, the C₁₀monoolefins of any feedstock described herein can have a molar ratio of4-ethyl-1-octene to 5-methyl-1-nonene of at least about 1.6:1,alternatively at least about 1.7:1, alternatively at least about 1.9:1,or alternatively at least about 2.1:1. In an embodiment, the C₁₀monoolefins of any feedstock described herein can have a molar ratio of2-butyl-1-hexene to 5-methyl-1-nonene of at least about 2:1,alternatively at least about 2.4:1, alternatively at least about 2.6:1,or alternatively at least about 2.8:1; a molar ratio of3-propyl-1-heptene to 5-methyl-1-nonene of at least about 1.2:1,alternatively at least about 1.4:1, alternatively at least about 1.6:1,or alternatively at least about 1.8:1; and a molar ratio of4-ethyl-1-octene to 5-methyl-1-nonene of at least about 1.6:1,alternatively at least about 1.7:1, alternatively at least about 1.9:1,or alternatively at least about 2.1:1.

In an embodiment, the C₁₀ monoolefins of any feedstock described herein(e.g., a first feedstock or a second feedstock) can comprise linear C₁₀monoolefins. In such embodiment, the linear C₁₀ monoolefins cancomprise, can consist essentially of, or can be, 1-decene, 4-decene,5-decene, or combinations thereof; alternatively, 1-decene;alternatively, 4-decene and/or 5-decene; alternatively, 4-decene; oralternatively, 5-decene. In an embodiment, the C₁₀ monoolefins of anyfeedstock described herein can comprise less than or equal to about 26mol %, alternatively less than or equal to about 24 mol %, alternativelyless than or equal to about 22 mol %, alternatively less than or equalto about 20 mol %, or alternatively less than or equal to about 18 mol %linear C₁₀ monoolefins. In an embodiment, the C₁₀ monoolefins of anyfeedstock described herein can comprise from about 1 mol % to about 16mol %, alternatively from about 2 mol % to about 15 mol %, alternativelyfrom about 3 mol % to about 14 mol %, alternatively from about 4 mol %to about 13 mol %, or alternatively from about 6 mol % to about 12 mol %4-decene and/or 5-decene. In some embodiments, the C₁₀ monoolefins ofany feedstock described herein can comprise less than or equal to about10 mol %, alternatively less than or equal to about 9 mol %,alternatively less than or equal to about 8 mol %, alternatively lessthan or equal to about 7 mol %, or alternatively less than or equal toabout 6 mol % 1-decene. In other embodiments, the C₁₀ monoolefins of anyfeedstock described herein can comprise from about 0.5 mol % to about 9mol %, alternatively from about 1 mol % to about 8 mol %, alternativelyfrom about 1.5 mol % to about 7 mol %, or alternatively from about 2 mol% to about 6 mol % l-decene.

In an embodiment, the first feedstock disclosed herein can furthercomprise C⁹⁻ monoolefins, C₁₁₊ monoolefins, or combinations thereof;alternatively, C⁹⁻ monoolefins; or alternatively, C₁₁₊ monoolefins. Inan embodiment, the C⁹⁻ monoolefins can comprise, can consist essentiallyof, or can be, a C₇ monoolefin, a C₈ monoolefin, a C₉ monoolefin, orcombinations thereof; alternatively, a C₇ monoolefin; alternatively, aC₈ monoolefin; or alternatively, a C₉ monoolefin. In some embodiments,the C⁹⁻ monoolefins can comprise, can consist essentially of, or can be,a C₈ monoolefin. In an embodiment, the C₁₁ monoolefins can comprise, canconsist essentially of, or can be, a C₁₁ monoolefin, a C₁₂ monoolefin, aC₁₃ monoolefin, a C₁₄ monoolefin, a C₁₅ monoolefin, a C₁₆ monoolefin, aC₁₇ monoolefin, a C₁₈ monoolefin, or combinations thereof;alternatively, a C₁₁ monoolefin; alternatively, a C₁₂ monoolefin;alternatively, a C₁₃ monoolefin; alternatively, a C₁₄ monoolefin;alternatively, a C₁₅ monoolefin; alternatively, a C₁₆ monoolefin;alternatively, a C₁₇ monoolefin; or alternatively, a C₁₈ monoolefin. Insome embodiments, the C₁₁₊ monoolefins can comprise, can consistessentially of, or can be, a C₁₂ monoolefin, a C₁₆ monoolefin, a C₁₈monoolefin, or combinations thereof; alternatively, a C₁₂ monoolefin;alternatively, a C₁₆ monoolefin; or alternatively, a C₁₈ monoolefin.

In an embodiment, the first feedstock disclosed herein can furthercomprise C₈ monoolefins, C₁₂ monoolefins, C₁₆ monoolefins, C₁₈monoolefins, or combinations thereof; alternatively, C₈ monoolefins;alternatively, C₁₂ monoolefins; alternatively, C₁₆ monoolefins and/orC₁₈ monoolefins; alternatively, C₁₆ monoolefins; or alternatively, C₁₈monoolefins. In an embodiment, the C₈ monoolefins can comprise 1-octene.In an embodiment, the C₁₂ monoolefins can comprise 1-dodecene.

In an embodiment, the first feedstock can further comprise from about0.1 mol % to about 5 mol %, alternatively from about 0.25 mol % to about4 mol %, or alternatively from about 0.5 mol % to about 3 mol % C₁₂monoolefins. In such embodiment, the C₁₂ monoolefins can comprise fromabout 54 mol % to about 74 mol %, alternatively from about 56 mol % toabout 72 mol %, alternatively from about 58 mol % to about 70 mol %, oralternatively from about 60 mol % to about 68 mol % 1-dodecene.

In an embodiment, the first feedstock can further comprise from about0.1 mol % to about 5 mol %, alternatively from about 0.25 mol % to about4 mol %, or alternatively from about 0.5 mol % to about 3 mol % C₈monoolefins. In such embodiment, the C₈ monoolefins can comprise atleast about 95 mol %, alternatively at least about 96 mol %,alternatively at least about 97 mol %, alternatively at least about 98mol %, or alternatively at least about 99 mol % 1-octene.

In an embodiment, the first feedstock can further comprise from about0.05 mol % to about 2 mol %, alternatively from about 0.04 mol % toabout 1.5 mol %, alternatively from about 0.06 mol % to about 1.25 mol%, alternatively from about 0.08 mol % to about 1 mol %, oralternatively from about 0.1 mol % to about 0.75 mol % C₁₆ monoolefinsand/or C₁₈ monoolefins.

In an embodiment, a feedstock comprising branched C₁₀ monoolefinsproduced in a 1-hexene process can be purified to produce a secondfeedstock of the type described herein, for example to improve olefinreactivity and resultant mercaptan and/or sulfide purity. A lightfraction, comprising C⁹⁻, can be removed from the feedstock and any C₁₀olefin isomers can be collected overhead to obtain a high purity (>95%)C₁₀ monoolefin fraction as the second feedstock. This high purity C₁₀monoolefin fraction (i.e., second feedstock) comprises little or nonon-olefin impurities or C₁₁ to C₁₇ compounds. The high purity C₁₀olefin can be reacted with H₂S to produce a crude composition. Reactionconditions to produce a crude composition from the high purity C₁₀monoolefin fraction (i.e., a second feedstock) can be identical to thereaction conditions disclosed for the feedstock comprising branched C₁₀monoolefins produced in a 1-hexene process used as received withoutfurther purification (i.e., a first feedstock). The major differencebetween reacting a first feedstock and a second feedstock is thecomposition of the crude composition and any resulting purified orpartially purified products (e.g., fractions or cuts taken from thecrude composition). For the second feedstock (e.g., a high purity (>95%)C₁₀ monoolefin fraction), the crude composition can comprise residualH₂S, unreacted C₁₀ olefin, C₁₀ mercaptan isomers, and C₁₀H₂₁—S—C₁₀H₂₁sulfides and minimal other mercaptans or sulfides. After removal of H₂Sand C⁹⁻ lights from the crude composition, the resultant partiallypurified product will contain C₁₀ mercaptan isomers and C₂₀ sulfides,but will not contain any of the intermediate mercaptans and asymmetricsulfide components formed by reactions of olefins having less than orgreater than 10 carbon atoms (because there were minimal, if any, sucholefins having less than or greater than 10 carbon atoms in the purifiedfeedstock). While not wishing to be bound by theory, it is believed thatthe intermediate mercaptans and asymmetric sulfide components can beproduced from the reaction of C₁₀ mercaptans with other non-C₁₀ olefins.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted at an H₂S to olefin molar ratio of fromabout 1:1 to about 20:1, alternatively from about 2:1 to about 15:1, oralternatively from about 3:1 to about 10:1.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted at a pressure of from about 30 psig (206kPag) to about 1,500 psig (10,300 kPag), alternatively from about 100psig (690 kPag) to about 1, 250 psig (8,600 kPag), or alternatively fromabout 250 psig (1,700 kPag) to about 1,000 psig (6,900 kPag).

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted to produce olefin conversion of equal toor greater than about 80%, alternatively equal to or greater than about85%, or alternatively equal to or greater than about 90%. For purposesof the disclosure herein, an olefin conversion refers to the mol % ofolefins that have reacted during the reaction between H₂S and afeedstock in a reactor, with respect to the amount of olefins introducedinto the reactor during the same time period.

In an embodiment, the process can comprise reacting H₂S and a feedstock(e.g., a first or second feedstock as described herein) comprising oneor more branched C₁₀ monoolefins in the presence of an initiating agentto produce a crude composition; wherein the initiating agent comprisesultraviolet (UV) radiation. In such embodiment, the UV radiation can beany UV radiation capable of initiating the reaction of the olefinspresent in the feedstock and H₂S. In some embodiments, the UV radiationcan be generated by a medium pressure mercury lamp. As will beappreciated by one of skill in the art, and with the help of thisdisclosure, although UV radiation can be the initiating agent, othersuitable types of light sources can be used.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an initiating agentcomprising UV radiation in a batch reactor or a continuous reactor.Nonlimiting examples of continuous reactors suitable for use in thepresent disclosure include continuous flow reactors, continuous stirredreactors, fixed bed reactors, and the like, or combinations thereof.Nonlimiting examples of batch reactors suitable for use in the presentdisclosure include UV batch reactors. As will be appreciated by one ofskill in the art, and with the help of this disclosure, any othersuitable type of batch and continuous reactors can be used for reactingH₂S and a feedstock comprising one or more branched C₁₀ monoolefins inthe presence of UV radiation. UV reactors and conditions suitable forreacting H₂S and a feedstock comprising one or more branched C₁₀monoolefins in the presence of UV radiation are described in more detailin U.S. Pat. No. 7,989,655, and U.S. Publication No. 20140221692 A1,each of which is incorporated by reference herein in its entirety.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of UV radiation in acontinuous reactor, the continuous reactor can be sized and configuredto the desired continuous production rate. That is, a person skilled inthe art will be able to select an appropriate reaction vessel size,geometry and material (e.g., a transparent material for sidewalls,windows, or internal chambers); along with an appropriate number of UVsources; and arrange the sources and reactor vessel (e.g., place UVsources adjacent a transparent exterior portion of the reaction vesseland/or disposed in transparent chambers within the reactor vessel) toyield a desired continuous production rate.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of UV radiation in a batchreactor, the batch reactor can be characterized by a reaction time offrom about 1 minute to about 4 hours, alternatively from about 10minutes to about 2 hours, or alternatively from about 30 minutes toabout 1.5 hours.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of UV radiation at atemperature of from about 0° C. to about 100° C., alternatively fromabout 10° C. to about 70° C., or alternatively from about 15° C. toabout 35° C.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of UV radiation at a H₂Sto olefin molar ratio of from about 1:1 to about 15:1, alternativelyfrom about 2:1 to about 12.5:1, or alternatively from about 5:1 to about10:1.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of aninitiating agent to produce a crude composition; wherein the initiatingagent comprises ultraviolet (UV) radiation, and wherein the initiatingagent further comprises a phosphite promoter, a photoinitiator, or both.

In an embodiment, the phosphite promoter can be used in an amount offrom about 0.01 wt. % to about 5 wt. %, alternatively from about 0.1 wt.% to about 4 wt. %, or alternatively from about 1 wt. % to about 2.5 wt.%, based on a weight of olefins.

In an embodiment, the phosphite promoter can be characterized by formulaP(OR⁵)₃, wherein each R⁵ can independently be a C₁-C₁₈ hydrocarbylgroup, alternatively C₁-C₁₀ hydrocarbyl group, alternatively C₁-C₅hydrocarbyl group; alternatively a C₁-C₁₈ alkyl group, alternativelyC₁-C₁₀ alkyl group, alternatively C₁-C₅ alkyl group; alternatively, aC₆-C₁₈ aryl group, or alternatively, a C₆-C₁₀ aryl group. Nonlimitingexamples of R⁵ groups suitable for use in the present disclosure in thephosphite promoter include a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group; a phenyl group, a tolylgroup, a xylyl group, a naphthyl group; and the like, or combinationsthereof.

Nonlimiting examples of phosphite promoters suitable for use in thepresent disclosure include a trialkylphosphite, trimethylphosphite,triethylphosphite, tributylphosphite; a triarylphosphite,triphenylphosphite; and the like, or combinations thereof.

In an embodiment, the photoinitiator can be used in an amount of fromabout 0.05 wt. % to about 5 wt. %, alternatively from about 0.1 wt. % toabout 4 wt. %, or alternatively from about 1 wt. % to about 2.5 wt. %,based on the weight of olefins present in the feed mixture.

Nonlimiting examples of photoinitiators suitable for use in the presentdisclosure include 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone,Bis-(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methy-1-propan-1-one,2-hydroxy-2-methyl-1-phenyl-1-propanone, and the like, or combinationsthereof.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of UVradiation to produce a crude composition (wherein the crude compositioncomprises from 50-100 wt. % C₁₀ mercaptans, alternatively from 50-90 wt.% C₁₀ mercaptans, alternatively from 75-85 wt. % C₁₀ mercaptans);wherein the C₁₀ mercaptans present in the crude composition furthercomprise from about 70 wt. % to about 100 wt. %, alternatively fromabout 70 wt. % to about 95 wt. %, alternatively from about 80 wt. % toabout 90 wt. %, or alternatively from about 79 wt. % to about 85 wt. %C₁₀ primary mercaptans; from about 0 wt. % to about 30 wt. %,alternatively from about 0 wt. % to about 20 wt. %, alternatively fromabout 10 wt. % to about 20 wt. %, or alternatively from about 5 wt. % toabout 19 wt. % C₁₀ secondary mercaptans; and from about 0 wt. % to about10 wt. %, alternatively from about 0 wt. % to about 5 wt. %, oralternatively from about 0 wt. % to about 3 wt. % C₁₀ tertiarymercaptans. For purposes of the disclosure herein, a primary mercaptanis a mercaptan that has the thiol group (—SH) attached to a primarycarbon (e.g., a carbon atom that is attached to one and only one othercarbon atom). Further, for purposes of the disclosure herein, asecondary mercaptan is a mercaptan that has the thiol group (—SH)attached to a secondary carbon (e.g., a carbon atom that is attached totwo and only two other carbon atoms). Further, for purposes of thedisclosure herein, a tertiary mercaptan is a mercaptan that has thethiol group (—SH) attached to a tertiary carbon (e.g., a carbon atomthat is attached to three and only three other carbon atoms). As will beappreciated by one of skill in the art, and with the help of thisdisclosure, the make-up of the crude composition, in terms of primary,secondary, and tertiary mercaptans, will depend on the make-up of thefeedstock, as well as on the reaction conditions. Further, as will beappreciated by one of skill in the art, and with the help of thisdisclosure, the make-up of each of the primary, secondary, and tertiarymercaptans will depend on the make-up of the feedstock, as well as onthe reaction conditions.

In an embodiment, the C₁₀ primary mercaptans can comprise5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),1-mercapto-decane (represented by Structure M), or combinations thereof.

In an embodiment, the C₁₀ secondary mercaptans can comprise4-mercapto-decane (represented by Structure N), 5-mercapto-decane(represented by Structure 0), 5-methyl-2-mercapto-nonane (represented byStructure E), 3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),2-mercapto-decane (represented by Structure P), or combinations thereof.

In an embodiment, the C₁₀ tertiary mercaptans can comprise equal to orgreater than about 90 wt. %, alternatively equal to or greater thanabout 95 wt. %, or alternatively equal to or greater than about 99 wt. %5-methyl-5-mercapto-nonane (represented by Structure H).

In an embodiment, the process can comprise reacting H₂S and a feedstock(e.g., a first or second feedstock as described herein) comprising oneor more branched C₁₀ monoolefins in the presence of an initiating agent(e.g., catalyst) to produce a crude composition; wherein the initiatingagent comprises an acid catalyst. Nonlimiting examples of acid catalystssuitable for use in the present disclosure include acid washed clays(such as, but not limited to, Filtrol® 24 or Filtrol® 24X); acid washedbentonite; a tetrafluoroethylene polymer resin modified withperfluorovinyl ether groups terminated with sulfonate groups; amacroreticular, sulfonated, crosslinked copolymer of styrene and divinylbenzene; and the like, or combinations thereof.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an acid catalyst in acontinuous reactor, such as for example continuous flow reactor,continuous stirred reactors, fixed bed reactors, packed bed reactors,and the like, or combinations thereof.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of an acid catalyst in acontinuous reactor, the continuous reactor can be characterized by aweight hourly space velocity (WHSV) of from about 0.1 h⁻¹ to about 5h⁻¹, alternatively from about 0.5 h⁻¹ to about 4 h⁻¹, or alternativelyfrom about 1 h⁻¹ to about 3 h⁻¹, based on mass of olefin per mass ofcatalyst per hour.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an acid catalyst at atemperature of from about 100° C. to about 300° C., alternatively fromabout 120° C. to about 220° C., or alternatively from about 180° C. toabout 200° C.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an acid catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of anacid catalyst to produce a crude composition (wherein the crudecomposition comprises from 50-100 wt. % C₁₀ mercaptans, alternativelyfrom 50-90 wt. % C₁₀ mercaptans, alternatively from 75-85 wt. % C₁₀mercaptans); wherein the C₁₀ mercaptans comprise from about 0 wt. % toabout 5 wt. % alternatively from about 0.1 wt. % to about 4 wt. %, oralternatively from about 0.5 wt. % to about 2.5 wt. % C₁₀ primarymercaptans; from about 80 wt. % to about 95 wt. %, alternatively fromabout 82.5 wt. % to about 92.5 wt. %, or alternatively from about 85 wt.% to about 90 wt. % C₁₀ secondary mercaptans; and from about 5 wt. % toabout 20 wt. %, alternatively from about 7.5 wt. % to about 17.5 wt. %,or alternatively from about 10 wt. % to about 15 wt. % C₁₀ tertiarymercaptans.

In an embodiment, the process can comprise reacting H₂S and a feedstock(e.g., a first or second feedstock as described herein) comprising oneor more branched C₁₀ monoolefins in the presence of an initiating agentto produce a crude composition; wherein the initiating agent comprises ahydrodesulfurization (HDS) catalyst.

In an embodiment, the HDS catalyst comprises a comprises a metal, atransition metal, Ru, Co, Mo, Ni, W, sulfides thereof, disulfidesthereof, and the like, or combinations thereof.

In an embodiment, the HDS catalyst can be Haldor Topsoe TK-554 orTK-570, and the like, or combinations thereof.

In an embodiment, the HDS catalyst can further comprise a support, suchas for example alumina, silica, and the like, or combinations thereof.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an HDS catalyst in acontinuous reactor, such as for example continuous flow reactor,continuous stirred reactors, fixed bed reactors, packed bed reactors,and the like, or combinations thereof.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of an HDS catalyst in acontinuous reactor, the continuous reactor can be characterized by aWHSV of from about 0.1 h⁻¹ to about 5 h⁻¹, alternatively from about 0.5h⁻¹ to about 4 h⁻¹, or alternatively from about 1 h⁻¹ to about 3 h⁻¹,based on mass of olefin per mass of catalyst per hour.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an HDS catalyst at atemperature of from about 100° C. to about 300° C., alternatively fromabout 120° C. to about 220° C., or alternatively from about 180° C. toabout 200° C.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an HDS catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of anHDS catalyst to produce a crude composition (wherein the crudecomposition comprises from 50-100 wt. % C₁₀ mercaptans, alternativelyfrom 50-90 wt. % C₁₀ mercaptans, alternatively from 75-85 wt. % C₁₀mercaptans); wherein the C₁₀ mercaptans comprise from about 5 wt. % toabout 30 wt. % alternatively from about 10 wt. % to about 25 wt. %, oralternatively from about 15 wt. % to about 20 wt. % C₁₀ primarymercaptans; from about 60 wt. % to about 75 wt. %, alternatively fromabout 62.5 wt. % to about 72.5 wt. %, or alternatively from about 65 wt.% to about 70 wt. % C₁₀ secondary mercaptans; and from about 5 wt. % toabout 15 wt. %, alternatively from about 7.5 wt. % to about 13.5 wt. %,or alternatively from about 9 wt. % to about 12 wt. % C₁₀ tertiarymercaptans.

As noted previously, any such feedstocks comprising one or more branchedC₁₀ monoolefins can be reacted with hydrogen sulfide (H₂S) in thepresence of an initiating agent to produce a crude composition, and thecrude composition can be further refined (e.g., distilled or otherwiseseparated into one or more fractions such as lights, intermediate, andheavies) to yield the various compositions described herein. Asdescribed in more detail herein, the type and/or amounts of theconstituent components that form the crude composition can varydepending upon the feedstock (e.g., the amount and types of olefinstherein), the reaction conditions, the catalysts employed, etc., and oneskilled in the art can tailor the post reactor processing of the crudecomposition to account for the specific compounds present in a givencrude composition to yield various desired products and compositions ofthe types described herein.

Upon completion of the reaction of a feedstock comprising one or morebranched C₁₀ monoolefins with hydrogen sulfide (H₂S), a reactor effluentcan be recovered from the reactor and H₂S removed therefrom to yield acrude composition. The term “crude composition” or “crude product”refers to an unrefined effluent stream recovered from the reactor afterremoval of H₂S, and in particular to an H₂S-free effluent stream thathas not undergone any additional post-reactor processing such asflashing, distillation, or other separation techniques or processes toremove any components from the effluent stream other than the initialremoval of H₂S.

Hydrogen sulfide (H₂S) is a highly corrosive, poisonous, flammable,explosive gas. As such, it is typically removed before the crudecomposition can be further processed or utilized. Bulk H₂S can beremoved under conditions of reduced pressure, and residual H₂S can beremoved at reduced temperature and pressure without removing anysubstantial quantities of the lights. Alternatively, H₂S can also beremoved by sparging inert gas into the liquid phase. Alternatively,there are other methods for removing H₂S (i.e., absorption, stripping,etc.) that are known to those of skill in the art. In an embodiment,under appropriate conditions, a reactor effluent can be treated toremove essentially all of any excess and/or unreacted hydrogen sulfide(H₂S).

The crude composition comprises branched C₁₀ mercaptans and branched C₂₀sulfides formed by the reaction of H₂S and the one or more branched C₁₀monoolefins, and the structures of these branched C₁₀ mercaptans andbranched C₂₀ sulfides are described in more detail herein. In additionto branched C₁₀ mercaptans and branched C₂₀ sulfides, the crudecomposition can comprise a number of other compounds such as unreactedolefins, inert compounds (e.g., alkanes), non-branched C₁₀ mercaptans,non-branched C₂₀ sulfides, non-C₁₀ mercaptans, non-C₂₀ sulfides, andother impurities. The constituent components contained within the crudecomposition can vary depending upon the composition of the feedstock(e.g., an unpurified first feedstock as compared to a purified secondfeedstock as described herein) as well as reaction conditions, catalyst,etc. In various embodiments, a crude composition can comprise light,intermediate, and heavy fractions as described herein.

In an embodiment, the crude compositions can contain a variety of othernon-C₁₀ mercaptan and non-C₂₀ sulfides components (e.g., impurities)such as C₈ mercaptans; C₁₂ mercaptans; C₁₄ mercaptans; C₁₆ mercaptans;C₁₈ mercaptans; C₁₆₋₃₆ sulfides represented by the structure R³—S—R⁴,wherein R³ and R⁴ are each independently a functional group derived froman olefin selected from the group consisting of C₈ monoolefins, C₁₀monoolefins, C₁₂ monoolefins, C₁₄ monoolefins, C₁₆ monoolefins, and C₁₈monoolefins, wherein R³ and R⁴ are not both branched C₁₀ monoolefins;unreacted C₈₋₁₈ monoolefins; non-olefin impurities selected from thegroup consisting of C₈₋₁₄ alkanes, cyclohexane, methylcyclopentane,methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene,hexamethylbenzene, C₄₋₁₂ alcohols, 2-ethyl-1-hexanol, and2-ethylhexyl-2-ethylhexanoate; and combinations thereof.

In an embodiment, a crude composition comprising branched C₁₀ mercaptansand branched C₂₀ sulfides can be separated by any process or unitoperation known in the art. For example, a crude composition can beprocessed (e.g., distilled) to remove a fraction of light compounds.Alternatively, a crude composition can be processed to recover both alights fraction and an intermediates fraction (e.g., a rough cut),followed by further processing to obtain one or more fine cuts.Alternatively, a crude composition can be processed to recover a heaviesfraction (e.g., a C₂₀ sulfide fraction). Alternatively, a crudecomposition can be processed to separate out any combination of a lightsfraction, an intermediates fraction (e.g., comprising C₁₀ mercaptans,including branched C₁₀ mercaptans), and a heavies fraction (e.g.,comprising C₂₀ sulfides, including branched C₂₀ sulfides). Furthermore,a light, intermediate or heavy fraction (e.g., a rough cut) can befurther processed or parsed to obtain one or more desired fine cuts(e.g., a C₁₀ mercaptan fraction). Alternatively, a crude composition canbe separated to produce a high-purity C₁₀ mercaptan stream and/or ahigh-purity C₂₀ sulfide stream (e.g., to obtain a desired fine cut orfraction such as a C₁₀ mercaptan fraction). Further, these separatedstreams can be blended in any combination of ratios to produce a mixturewith specific concentrations of one of more components (e.g., desiredblend ratios of branched C₁₀ mercaptans and/or branched C₂₀ sulfides,for example to aid in a particular end use). The unitoperations/processes used for these separations are known to one ofskill and the art and include, but are not limited to, distillation,fractionation, flashing, stripping, and absorption, and others. The unitoperation conditions, such as for example, temperature, pressure, flowrates, and others at which these unit operations produce one or more ofthe desired fractions can easily be determined by one of ordinary skillin the art.

In an embodiment, a lights fraction is removed from the crudecomposition, for example by flashing, distillation, fractionation,stripping, absorption, etc.

In an embodiment, the lights fraction can comprise at least about 90 wt.%, alternatively at least about 90 wt. %, alternatively at least about95 wt. %, alternatively at least about 96 wt. %, alternatively at leastabout 97 wt. %, alternatively at least about 98 wt. %, alternatively atleast about 99 wt. % C⁹⁻ compounds, based on the total weight of thelights fraction. Nonlimiting examples of C⁹⁻ compounds include C⁹⁻monoolefins (e.g., unreacted C⁹⁻ monoolefins), C⁹⁻ mercaptans, C⁹⁻alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene,toluene, ethylbenzene, xylene, mesitylene, C⁹⁻ alcohols,2-ethyl-1-hexanol, and the like, or combinations thereof. In anembodiment, the lights fraction can comprise less than about 10 wt. %,alternatively less than about 5 wt. %, alternatively less than about 4wt. %, alternatively at less than about 3 wt. %, alternatively less thanabout 2 wt. %, alternatively less than about 1 wt. % C₁₀₊ compounds,based on the total weight of the lights fraction.

In an embodiment, the C⁹⁻ monoolefins can comprise, can consistessentially of, or can be, a C₇ monoolefin, a C₈ monoolefin, a C₉monoolefin, or combinations thereof; alternatively, a C₇ monoolefin;alternatively, a C₈ monoolefin; or alternatively, a C₉ monoolefin. Insome embodiments, the C⁹⁻ monoolefins can comprise, can consistessentially of, or can be, a C₈ monoolefin (e.g., 1-octene).

In an embodiment, the C⁹⁻ mercaptans can comprise, can consistessentially of, or can be, a C₇ mercaptan, a C₈ mercaptan, a C₉mercaptan, or combinations thereof; alternatively, a C₇ mercaptan;alternatively, a C₈ mercaptan; or alternatively, a C₉ mercaptan. In someembodiments, the C⁹⁻ mercaptans can comprise, can consist essentiallyof, or can be, a C₈ mercaptan.

Following removal of the lights (for example, via flash), a combinedintermediate and heavy fraction (i.e., C₁₀₊ compounds sometimes referredto as a kettle product in the Examples) can remain, and the combinedintermediate and heavy fraction can be used “as is” or can be furtherprocessed, for example separated or split into separate intermediate andheavy fractions (and said separate intermediate and heavy fractions canbe subsequently recombined in various blends and associated blendratios), as described in more detail herein. In an embodiment, acombined intermediate and heavy fraction (i.e., C₁₀₊ compounds) formedby removal of the lights fraction from the crude composition cancomprise less than about 15 wt. %, alternatively less than about 10 wt.%, alternatively less than about 9 wt. %, alternatively less than about8 wt. %, alternatively less than about 7 wt. %, alternatively less thanabout 6 wt. %, alternatively less than about 5 wt. %, alternatively lessthan about 4 wt. %, alternatively less than about 3 wt. %, alternativelyless than about 2 wt. %, alternatively less than about 1 wt. % C⁹⁻products, based on the total weight of the combined intermediate andheavy fraction (i.e., C₁₀₊ compounds).

In an embodiment, a combined intermediate and heavy fraction (i.e., C₁₀₊compounds) can comprise (A) at least about 50 wt. %, alternatively atleast about 60 wt. %, alternatively at least about 70 wt. %,alternatively at least about 80 wt. %, alternatively at least about 90wt. %, alternatively at least about 95 wt. %, or alternatively at leastabout 99 wt. % mercaptans; wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of themercaptans can be branched C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least about 10 wt. %, alternatively atleast about 15 wt. %, alternatively at least about 20 wt. %,alternatively at least about 25 wt. % sulfides, or alternatively atleast about 30 wt. % sulfides; wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of the sulfidescan be branched C₂₀ sulfides represented by structure R¹—S—R², whereinboth R¹ and R² can each independently be a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene (representedby Structure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), or combinations thereof.

In an embodiment, the crude composition can be flashed to remove alights fraction as described herein to produce a combined intermediateand heavy fraction (i.e., C₁₀₊ compounds) comprising: (A) at least about25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. % C₁₀ branchedmercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 15 wt. %,alternatively at least about 20 wt. %, alternatively at least about 25wt. %, or alternatively at least about 30 wt. % branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein both R¹ and R² can eachindependently be a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

In an embodiment, the crude composition can be flashed to remove alights fraction as described herein to produce a combined intermediateand heavy fraction (i.e., C₁₀₊ compounds) comprising: (A) from at leastabout 50 wt. % to at least about 90 wt. %, alternatively from at leastabout 55 wt. % to at least about 85 wt. %, or alternatively from atleast about 60 wt. % to at least about 80 wt. % mercaptans, wherein atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the mercaptans can be branched C₁₀ mercaptans selectedfrom the group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) from at least about 10 wt. % to at leastabout 30 wt. %, alternatively from at least about 10 wt. % to at leastabout 25 wt. %, alternatively from at least about 12.5 wt. % to at leastabout 22.5 wt. %, or alternatively from at least about 15 wt. % to atleast about 20 wt. % sulfides; wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of the sulfidescan be branched C₂₀ sulfides represented by structure R¹—S—R², whereinboth R¹ and R² can each independently be a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene (representedby Structure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), or combinations thereof.

In an embodiment, the crude composition can be flashed to remove alights fraction and subsequently further separated to produce anintermediate fraction and a heavies fraction. The intermediate fractionand the heavies fractions can then be optionally further processed(e.g., polished) and mixed in any appropriate ratio to produce a blendedcomposition comprising: (A) at least about 25 wt. %, alternatively atleast about 30 wt. %, alternatively at least about 40 wt. %,alternatively at least about 50 wt. %, alternatively at least about 80wt. %, or alternatively at least about 90 wt. % C₁₀ mercaptans (e.g.,branched C₁₀ mercaptans) selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; (B) at least about 5 wt. %, alternatively at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, alternatively at least about 25 wt. %, oralternatively at least about 30 wt. % C₂₀ sulfides (e.g., branched C₂₀sulfides) represented by structure R¹—S—R², wherein R¹ and R² can eachindependently be a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof; and one or more of the following components(C)-(I): (C) less than about 5 wt. %, alternatively less than about 4wt. %, alternatively less than about 3 wt. %, alternatively less thanabout 2 wt. %, or alternatively less than about 1 wt. % C₈ mercaptans;(D) less than about 15 wt. %, alternatively less than about 10 wt. %, oralternatively less than about 5 wt. % C₁₂ mercaptans; (E) less thanabout 15 wt. %, alternatively less than about 10 wt. %, or alternativelyless than about 5 wt. % C₁₄ mercaptans; (F) less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively less than about 3wt. %, alternatively less than about 2 wt. %, or alternatively less thanabout 1 wt. % C₁₆ mercaptans and/or C₁₈ mercaptans; (G) less than about1 wt. %, alternatively less than about 0.5 wt. %, alternatively lessthan about 0.4 wt. %, alternatively less than about 0.3 wt. %,alternatively less than about 0.2 wt. %, or alternatively less thanabout 0.1 wt. % C₁₆₋₃₆ sulfides represented by the structure R³—S—R⁴,wherein R³ and R⁴ are each independently a functional group derived froman olefin selected from the group consisting of C₈ monoolefins, C₁₀monoolefins, C₁₂ monoolefins, C₁₄ monoolefins, C₁₆ monoolefins, and C₁₈monoolefins, wherein R³ and R⁴ are not both branched C₁₀ monoolefins;(H) less than about 10 wt. %, alternatively less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively less than about 3wt. %, alternatively less than about 2 wt. %, or alternatively less thanabout 1 wt. % unreacted C₈₋₁₈ monoolefins; and (I) less than about 10wt. %, alternatively less than about 5 wt. %, alternatively less thanabout 4 wt. %, alternatively less than about 3 wt. %, alternatively lessthan about 2 wt. %, or alternatively less than about 1 wt. % non-olefinimpurities selected from the group consisting of C₈₋₁₄ alkanes,cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene,ethylbenzene, xylene, mesitylene, hexamethylbenzene, C₄₋₁₂ alcohols,2-ethyl-1-hexanol, and 2-ethylhexyl-2-ethylhexanoate. In variousembodiments, the blended composition can comprise varying amounts ofeach of components (C)—(I), and the presence of each component (C)-(I)and the amount thereof can be independently formulated and/orcontrolled. In various embodiments, the blended composition can comprisean amount of one or more components (C)-(I) that is greater than zero(i.e., above a detection limit associated with the component) and lessthan the upper range endpoint set forth above (e.g., component (C) ispresent in the composition in an amount greater than zero and less thanabout 5 wt. %, and so forth as set forth above).

In some embodiments, a mercaptan/sulfide composition of the typedisclosed herein can be prepared by combining at least a portion of afirst mercaptan/sulfide composition (wherein only a lights fraction hasbeen removed from the crude product to yield a combined intermediate andheavy fraction, e.g., C₁₀₊ compounds) with at least a portion of aheavies fraction comprising a sulfide composition to yield a secondmercaptan/sulfide composition, wherein a sulfide content of the secondmercaptan/sulfide composition is greater than a sulfide content of thefirst mercaptan/sulfide composition.

In an embodiment, the crude can be separated into light, intermediate,and heavy fractions by distillation, for example in a singledistillation column having a light fraction recovered as an overheadstream, an intermediate fraction (e.g., comprising branched C₁₀mercaptans) recovered as a side stream, and a heavy fraction (e.g.,comprising branched C₂₀ sulfides) recovered as a bottom stream. Inalternative embodiments, the separation can be in sequential steps suchas removal of the lights fraction in a first distillation column,followed by separation of the intermediate fraction (e.g., comprisingbranched C₁₀ mercaptans) as an overhead stream in a second distillationcolumn and the heavy fraction (e.g., comprising C₁₁₊ compounds,including branched C₂₀ sulfides) as a bottom stream of the seconddistillation column. These “rough-cut” light, intermediate, and heavystreams can be used “as is” or they can be further processed (e.g.,further refined or polished, for example by additional distillation orother separation techniques to produce “fine-cuts”) and/or blended toobtain a variety of products that are salable or otherwise available fora variety of end uses such as mining ore collector compositions or chaintransfer agents. For example, a variety of mercaptan compositions,sulfide compositions, and mixed mercaptan/sulfide compositions can beproduced of the type disclosed in more detail herein.

In an embodiment, an intermediate fraction can comprise at least about25 wt. %, alternatively at least about 30 wt. %, alternatively at leastabout 40 wt. %, alternatively at least about 50 wt. % branched C₁₀mercaptans, alternatively at least about 75 wt. % branched C₁₀mercaptans, or alternatively at least about 85 wt. % branched C₁₀mercaptans. In such embodiment, the branched C₁₀ mercaptans can beselected from the group consisting of 5-methyl-1-mercapto-nonane(represented by Structure A), 3-propyl-1-mercapto-heptane (representedby Structure B), 4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In an embodiment, the heavy fraction can comprise at least about 5, 10,15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. %,branched C₂₀ sulfides represented by structure R¹—S—R², wherein both R¹and R² are each independently a branched C₁₀ alkyl group derived fromthe branched C₁₀ monoolefin, and wherein the branched C₁₀ alkyl group isselected from the group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ sulfide.

In an embodiment, a mercaptan composition can comprise mercaptans,wherein at least a portion of the mercaptans comprise C₁₀ mercaptans,and wherein at least a portion of the C₁₀ mercaptans comprise branchedC₁₀ mercaptans. In an embodiment, the branched C₁₀ mercaptans cancomprise 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), or combinationsthereof.

For purposes of the disclosure herein, branched C₁₀ mercaptans refer tomercaptans (or thiols) that are characterized by the general formulaR—SH, wherein R is a branched alkyl group (as opposed to a linear alkylgroup), i.e., an alkyl group substituted with alkyl substituents; andwherein R has a total of 10 carbon atoms. Further, for purposes of thedisclosure herein, a composition comprising mercaptans, wherein at leasta portion of the mercaptans are branched C₁₀ mercaptans (e.g.,5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), or combinationsthereof), can also be referred to as a “branched C₁₀ mercaptancomposition.” In an embodiment, the mercaptan composition can compriseany suitable amount of branched C₁₀ mercaptans.

In an embodiment, the C₁₀ mercaptans can further comprise non-branchedC₁₀ mercaptans, such as for example 1-mercapto-decane (represented byStructure M), 4-mercapto-decane (represented by Structure N),5-mercapto-decane (represented by Structure 0), 2-mercapto-decane(represented by Structure P), or combinations thereof.

In some embodiments, a mercaptan composition can comprise mercaptans,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of themercaptans can be branched C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In other embodiments, a mercaptan composition can comprise at leastabout 1 wt. %, alternatively at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % mercaptans, wherein at least a portion of the mercaptans can bebranched C₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In yet other embodiments, a mercaptan composition can comprise at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % mercaptans; wherein atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at least85 wt. % of the mercaptans can be branched C₁₀ mercaptans selected fromthe group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In yet other embodiments, a mercaptan composition can comprise at leastabout 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. % mercaptans;wherein at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 95, or 99 wt. % of the mercaptans can be branched C₁₀ mercaptansselected from the group consisting of 5-methyl-1-mercapto-nonane(represented by Structure A), 3-propyl-1-mercapto-heptane (representedby Structure B), 4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a mercaptan composition can comprisefrom at least about 50 wt. % to at least about 90 wt. %, alternativelyfrom at least about 55 wt. % to at least about 85 wt. %, oralternatively from at least about 60 wt. % to at least about 80 wt. %mercaptans, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the mercaptans can be branchedC₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a mercaptan composition can consist ofor consist essentially of branched C₁₀ mercaptans selected from thegroup consisting of 5-methyl-1-mercapto-nonane (represented by StructureA), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a mercaptan composition can comprise atleast about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % branched C₁₀ mercaptans selected fromthe group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a composition can comprise mercaptans,wherein at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of the mercaptans are branched C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In an embodiment, a sulfide composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀ sulfides, and wherein atleast a portion of the C₂₀ sulfides comprise branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein R¹ and R² can eachindependently be an alkyl group, and wherein at least a portion of thealkyl groups comprises a branched C₁₀ alkyl group. In an embodiment, thealkyl group (e.g., a branched C₁₀ alkyl group as R¹, R²) can comprise afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

For purposes of the disclosure herein a sulfide will be referred to bythe total number of carbon atoms (as opposed to the number of carbons ofonly one of the alkyl groups present in a dialkyl sulfide). For example,a H₂₁C₁₀—S—C₁₀H₂₁ sulfide will be referred to as a C₂₀ sulfide (ratherthan a C₁₀ sulfide). For purposes of the disclosure herein, branched C₂₀sulfides refer to sulfides (or thioethers) that are characterized by thegeneral formula R¹—S—R², wherein both R¹ and R² are each independently abranched C₁₀ alkyl group (as opposed to a linear alkyl group), i.e., analkyl group substituted with alkyl substituents. Stated alternatively,branched C₂₀ sulfides refer to sulfides wherein both R¹ and R² arebranched C₁₀ alkyl groups, wherein R¹ and R² can be the same ordifferent. Further, for purposes of the disclosure herein, a compositioncomprising sulfides, wherein at least a portion of the sulfides arebranched C₂₀ sulfides represented by structure R¹—S—R², wherein both R¹and R² are each independently an alkyl group, wherein at least a portionof the alkyl group comprises a branched C₁₀ alkyl group (e.g., afunctional group derived from an olefin, and wherein the olefincomprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof), can also be referred to as a “branched C₂₀sulfide composition.” In an embodiment, the sulfide composition cancomprise any suitable amount of branched C₂₀ sulfides.

In an embodiment, a sulfide composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀ sulfides, and wherein atleast a portion of the C₂₀ sulfides comprise branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein both R¹ and R² can eachindependently be a branched C₁₀ alkyl group derived from a branched C₁₀monoolefin, and wherein the branched C₁₀ alkyl group is selected fromthe group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ sulfide. In an embodiment, the branched C₁₀ monoolefin can comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof. Generally, a monoolefin is a linear or branched aliphatichydrocarbon olefin that has one and only one carbon-carbon double bond.Generally, a C_(n) monoolefin is a linear or branched aliphatichydrocarbon olefin that has n and only n carbon atoms, and one and onlyone carbon-carbon double bond. A C₁₀ monoolefin is a linear or branchedaliphatic hydrocarbon olefin that has ten and only ten carbon atoms, andone and only one carbon-carbon double bond. A branched C₁₀ monoolefin isa branched aliphatic hydrocarbon olefin that has ten and only ten carbonatoms, and one and only one carbon-carbon double bond.

In an embodiment, the C₂₀ sulfides can further comprise non-branched C₂₀sulfides and/or partially branched C₂₀ sulfides represented by structureR¹—S—R², wherein both R¹ and R² (in the case of non-branched C₂₀sulfides) or one of the R¹ and R² (in the case of partially-branched C₂₀sulfides) can be a linear C₁₀ alkyl group derived from a linear C₁₀monoolefin, such as for example 4-decene (represented by Structure Q),5-decene (represented by Structure R), 1-decene (represented byStructure S), or combinations thereof.

For purposes of the disclosure herein, the non-branched C₂₀ sulfidesrepresented by structure R¹—S—R² are the sulfides wherein both R¹ and R²are each independently a linear C₁₀ alkyl group derived from a linearC₁₀ monoolefin. Further, for purposes of the disclosure herein, thepartially branched C₂₀ sulfides represented by structure R¹—S—R² are thesulfides wherein one of the R¹ and R² is a linear C₁₀ alkyl groupderived from a linear C₁₀ monoolefin, while the other one of the R¹ andR² is a branched C₁₀ alkyl group derived from a branched C₁₀ monoolefinas described herein.

In some embodiments, a sulfide composition can comprise sulfides,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of the sulfidescan be branched C₂₀ sulfides represented by structure R¹—S—R², whereinboth R¹ and R² can each independently be a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene (representedby Structure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), or combinations thereof.

In other embodiments, a sulfide composition can comprise at least about1 wt. %, alternatively at least about 5 wt. %, alternatively at leastabout 10 wt. %, alternatively at least about 20 wt. %, alternatively atleast about 30 wt. %, alternatively at least about 40 wt. %,alternatively at least about 50 wt. %, alternatively at least about 60wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. % sulfides,wherein at least a portion of the sulfides can be branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein both R¹ and R² can eachindependently be a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

In other embodiments, a sulfide composition can comprise at least about1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85,90, 95, or 99 wt. %, sulfides, wherein at least about 1, 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. %of the sulfides can be branched C₂₀ sulfides represented by structureR¹—S—R², wherein both R¹ and R² can each independently be a functionalgroup derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In yet other embodiments, a sulfide composition can comprise at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, or alternatively at least about 25 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ sulfides representedby structure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition can comprise fromat least about 10 wt. % to at least about 30 wt. %, alternatively fromat least about 12.5 wt. % to at least about 22.5 wt. %, or alternativelyfrom at least about 15 wt. % to at least about 20 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ sulfides representedby structure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition can consist of orconsist essentially of branched C₂₀ sulfides represented by structureR¹—S—R², wherein both R¹ and R² can each independently be a functionalgroup derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition can comprise atleast about 5 wt. %, alternatively at least about 10 wt. %,alternatively at least about 15 wt. %, or alternatively at least about20 wt. % C₂₀ sulfides (e.g., branched C₂₀ sulfides) represented bystructure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition comprises at leastabout 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 95, or 99 wt. % branched C₂₀ sulfides represented by thestructure R¹—S—R², wherein R¹ and R² are each independently a functionalgroup derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In an embodiment, a mercaptan/sulfide composition can comprise one ormore mercaptans and one or more sulfides of the type disclosed herein.For purposes of the disclosure herein, a composition comprising (i)mercaptans, wherein at least a portion of the mercaptans are branchedC₁₀ mercaptans, and (ii) sulfides, wherein at least a portion of thesulfides are branched C₂₀ sulfides, can also be referred to as a“branched C₁₀ mercaptan/C₂₀ sulfide composition.” In an embodiment, themercaptan/sulfide composition can comprise any suitable amount ofbranched C₁₀ mercaptans, and any suitable amount of branched C₂₀sulfides.

In an embodiment, a mercaptan/sulfide composition can comprise (A) atleast about 1 wt. %, alternatively at least about 5 wt. %, alternativelyat least about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % mercaptans, wherein at least a portion of the mercaptans can bebranched C₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least about 1 wt. %, alternatively atleast about 5 wt. %, alternatively at least about 10 wt. %,alternatively at least about 20 wt. %, alternatively at least about 30wt. %, alternatively at least about 40 wt. %, alternatively at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % sulfides, wherein atleast a portion of the sulfides can be branched C₂₀ sulfides representedby structure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In an embodiment, a mercaptan/sulfide composition can comprise C₁₀mercaptans represented by the general formula R—SH and/or C₂₀ sulfidesrepresented by structure R¹—S—R² that are formed by reacting an olefinfeedstock comprising olefins with H₂S as described in more detailherein, wherein the olefins present in the olefin feedstock provide thealkyl group represented by R, R¹, and R². In such embodiments, the Rgroup of the C₁₀ mercaptans and/or the R¹ and R² groups of the C₂₀sulfides are provided by or derived from the counterpart R, R¹, and R²groups present in the olefins in the olefin feedstock. In an embodiment,R, R¹ and R² can each independently be an alkyl group, wherein at leasta portion of the alkyl groups can comprise a functional group derivedfrom an olefin, wherein the olefin is present in a feedstock (e.g., afirst feedstock as described herein) comprising a) at least about 76 mol%, alternatively at least about 78 mol %, alternatively at least about80 mol %, or alternatively at least about 82 mol % C₁₀ monoolefins; andb) at least about 1 mol %, alternatively at least about 2 mol %,alternatively at least about 3 mol %, or alternatively at least about 4mol % C₁₄ monoolefins. In such embodiment, the C₁₀ monoolefins cancomprise i) at least about 3 mol %, alternatively at least about 4 mol%, alternatively at least about 5 mol %, alternatively at least about 6mol %, alternatively at least about 7 mol %, or alternatively at leastabout 8 mol % 2-butyl-1-hexene (represented by Structure L), ii) atleast about 8 mol %, alternatively at least about 9 mol %, alternativelyat least about 10 mol %, alternatively at least about 11 mol %,alternatively at least about 12 mol %, or alternatively at least about13 mol % 3-propyl-1-heptene (represented by Structure J), iii) at leastabout 6 mol %, alternatively at least about 7 mol %, alternatively atleast about 8 mol %, alternatively at least about 9 mol %, alternativelyat least about 10 mol %, or alternatively at least about 11 mol %4-ethyl-1-octene (represented by Structure K), and iv) at least about 20mol %, alternatively at least about 22 mol %, alternatively at leastabout 24 mol %, alternatively at least about 26 mol %, alternatively atleast about 28 mol %, or alternatively at least about 30 mol %5-methyl-1-nonene (represented by Structure I). In an embodiment, theC₁₀ monoolefins can comprise from about 1 mol % to about 16 mol %,alternatively from about 2 mol % to about 15 mol %, alternatively fromabout 3 mol % to about 14 mol %, alternatively from about 4 mol % toabout 13 mol %, or alternatively from about 6 mol % to about 12 mol %4-decene and/or 5-decene. In an embodiment, the C₁₀ monoolefins cancomprise from about 0.5 mol % to about 9 mol %, alternatively from about1 mol % to about 8 mol %, alternatively from about 1.5 mol % to about 7mol %, or alternatively from about 2 mol % to about 6 mol % 1-decene.

In an embodiment, the olefin (e.g., corresponding to R, R¹ or R²)present in the olefin feedstock (e.g., a first feedstock as describedherein) can further comprise from about 0.1 mol % to about 5 mol %,alternatively from about 0.25 mol % to about 4 mol %, or alternativelyfrom about 0.5 mol % to about 3 mol % C₁₂ monoolefins. In suchembodiment, the C₁₂ monoolefins can comprise from about 54 mol % toabout 74 mol %, alternatively from about 56 mol % to about 72 mol %,alternatively from about 58 mol % to about 70 mol %, or alternativelyfrom about 60 mol % to about 68 mol % 1-dodecene.

In an embodiment, the olefin (e.g., corresponding to R, R¹ or R²)present in the olefin feedstock (e.g., a first feedstock as describedherein) can further comprise from about 0.1 mol % to about 5 mol %,alternatively from about 0.25 mol % to about 4 mol %, or alternativelyfrom about 0.5 mol % to about 3 mol % C₈ monoolefins. In suchembodiment, the C₈ monoolefins can comprise at least about 95 mol %,alternatively at least about 96 mol %, alternatively at least about 97mol %, alternatively at least about 98 mol %, or alternatively at leastabout 99 mol % 1-octene.

In an embodiment, the olefin (e.g., corresponding to R, R¹ or R²)present in the olefin feedstock (e.g., a first feedstock as describedherein) can further comprise from about 0.05 mol % to about 2 mol %,alternatively from about 0.04 mol % to about 1.5 mol %, alternativelyfrom about 0.06 mol % to about 1.25 mol %, alternatively from about 0.08mol % to about 1 mol %, or alternatively from about 0.1 mol % to about0.75 mol % C₁₆ monoolefins and/or C₁₈ monoolefins.

In an embodiment where the R group of the C₁₀ mercaptans and/or the R¹and R² groups of the C₂₀ sulfides are provided by or derived from thecounterpart R, R¹, and R² groups present in the olefins in the olefinfeedstock (e.g., a first feedstock obtained from a 1-hexene process asdescribed herein), the resultant mercaptan/sulfide composition can be acrude composition that can be further separated and refined into othercompositions as described herein.

In an embodiment, mercaptan compositions, sulfide compositions, and/ormercaptan/sulfide compositions as disclosed herein advantageouslydisplay improvements in one or more composition characteristics whencompared to otherwise similar compositions lacking branched C₁₀mercaptans.

In an embodiment, a mercaptan composition and/or a mercaptan/sulfidecomposition comprising equal to or greater than about 25 wt. % C₁₀branched mercaptans as disclosed herein can advantageously have an odorless unpleasant and less offensive than an odor of an otherwise similarcomposition comprising equal to or greater than about 25 wt. % n-decylmercaptan, as perceived by equal to or greater than about 51% of humansubjects exposed to the odor of each composition.

In an embodiment, a mercaptan composition and/or a mercaptan/sulfidecomposition comprising equal to or greater than about 25 wt. % C₁₀branched mercaptans as disclosed herein can advantageously have an odorless unpleasant than an odor of an otherwise similar compositioncomprising equal to or greater than about 25 wt. % n-dodecyl mercaptanand/or tert-dodecyl mercaptan, as perceived by equal to or greater thanabout 51% of human subjects exposed to the odor of each composition.Additional advantages of the mercaptan compositions, sulfidecompositions, and/or mercaptan/sulfide compositions and processes ofproducing same as disclosed herein can be apparent to one of skill inthe art viewing this disclosure.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore C₁₁₊ monoolefins in the presence of an initiating agent, aspreviously described herein for the branched C₁₀ monoolefins, to producea crude composition (also referred to as a crude product); wherein thecrude composition comprises C₁₁₊ mercaptans and C₂₂₊ sulfides.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore C₁₁₊ monoolefins in the presence of an initiating agent, aspreviously described herein for the branched C₁₀ monoolefins, to producea C₁₁₊ mercaptans crude composition; wherein the C₁₁₊ monoolefinscomprise C₁₁ and C₁₂ internal monoolefins, C₁₃ and C₁₄ internalmonoolefins, C₁₄ and C₁₆ linear alpha monoolefins, and the like, orcombinations thereof.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore C₁₁₊ monoolefins in the presence of an initiating agent, aspreviously described herein for the branched C₁₀ monoolefins, to producea C₁₁₊ mercaptans crude composition; wherein the one or more C₁₁₊monoolefins is selected from the group consisting of C₁₁ and C₁₂internal monoolefins, C₁₃ and C₁₄ internal monoolefins, C₁₄ and C₁₆linear alpha monoolefins, and combinations thereof.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore C₁₁₊ monoolefins in the presence of an initiating agent, aspreviously described herein for the branched C₁₀ monoolefins, to producea C₁₁₊ mercaptans crude composition; wherein the one or more C₁₁₊monoolefins is selected from the group consisting of C₁₁ and C₁₂internal monoolefins, C₁₃ and C₁₄ internal monoolefins, and C₁₄ and C₁₆linear alpha monoolefins.

The sulfur source can be any sulfur source suitable to provide sulfurfor the conversion of olefins (e.g., C₁₁₊ monoolefins) to mercaptans(e.g., C₁₁₊ mercaptans) and sulfides (e.g., C₂₂₊ sulfides). The sulfursource can comprise H₂S, thioacetic acid, and the like, or combinationsthereof. In some aspects, the sulfur source can comprise H₂S, aspreviously described herein.

In an aspect, the feedstock can comprise C₁₁ and C₁₂ internalmonoolefins. Any feedstock comprising C₁₁ and C₁₂ internal monoolefinsof the type described herein can be used, for example a feedstockobtained from a commercial petroleum refining or petrochemical process.Such feedstocks can comprise other olefins in addition to the C₁₁ andC₁₂ internal monoolefins of the type described herein, for example C¹⁰⁻monoolefins, as well as C₁₃₊ monoolefins. An example of a C₁₁ and C₁₂internal monoolefins feedstock suitable for use in the presentdisclosure include NEODENE 1112 IO higher olefins, which contains acombination of C₁₁ and C₁₂ internal olefins that is commerciallyavailable from Shell Chemicals. A typical composition of NEODENE 1112 IOhigher olefins is given in the table below:

Component of NEODENE 1112 IO Unit Value Method C₁₀ & Lower (C₁₀₋) % m/m<1.5 SMS* 2976 [% mass/mass] C₁₁ % m/m 35-56 SMS 2976 C₁₂ % m/m 43-64SMS 2976 C₁₃ & Higher (C₁₃₋) % m/m <2.0 SMS 2976 Appearance Clear andVisual substantially free of visual impurities Color, Pt•Co <10 ASTMD1209- 05(2011) Water mg/kg <100 ASTM E1064-16 *SMS = Shell ModifiedSpot Test.

In an aspect, the feedstock can comprise at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, alternatively at least about 85 wt. %, alternatively at leastabout 90 wt. %, or alternatively at least about 95 wt. % C₁₁ and C₁₂internal monoolefins, based on the total weight of the feedstock. Insuch aspect, the feedstock can comprise (a) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about1.5 wt. % C¹⁰⁻ monoolefins; and (b) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2 wt. % C₁₃₊ monoolefins; based on the total weight of the feedstock.For purposes of the disclosure herein, a feedstock comprising at leastabout 70 wt. % C₁₁ and C₁₂ internal monoolefins, based on the totalweight of the feedstock, can also be referred to as a “first C₁₁ and C₁₂feedstock.”

In another aspect, the feedstock can comprise at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % C₁₁ and C₁₂ internal monoolefins, based on the totalweight of the feedstock. For purposes of the disclosure herein, afeedstock comprising at least about 95 wt. % C₁₁ and C₁₂ internalmonoolefins, based on the total weight of the feedstock, can also bereferred to as a “second C₁₁ and C₁₂ feedstock.” In an aspect, thesecond C₁₁ and C₁₂ feedstock can be produced by purifying the first C₁₁and C₁₂ feedstock, such as for example by distillation of the first C₁₁and C₁₂ feedstock.

In some aspects, the C₁₁ internal monoolefins and C₁₂ internalmonoolefins of any feedstock described herein (e.g., a first C₁₁ and C₁₂feedstock or a second C₁₁ and C₁₂ feedstock) can comprise linear C₁₁internal monoolefins and linear C₁₂ internal monoolefins, respectively.

In other aspects, the C₁₁ internal monoolefins and C₁₂ internalmonoolefins of any feedstock described herein (e.g., a first C₁₁ and C₁₂feedstock or a second C₁₁ and C₁₂ feedstock) can comprise branched C₁₁internal monoolefins and branched C₁₂ internal monoolefins,respectively. The branched C₁₁ internal monoolefins can comprise methylbranches. The branched C₁₂ internal monoolefins can comprise methylbranches.

In yet other aspects, the C₁₁ and C₁₂ internal monoolefins can compriselinear C₁₁ internal monoolefins, linear C₁₂ internal monoolefins,branched C₁₁ internal monoolefins, branched C₁₂ internal monoolefins, orcombinations thereof.

In some aspects, the feedstock can comprise (A) at least about 30 wt. %,alternatively at least about 35 wt. %, or alternatively at least about40 wt. % C₁₁ internal monoolefins, and (B) at least about 40 wt. %,alternatively at least about 45 wt. %, alternatively at least about 50wt. % C₁₂ internal monoolefins, based on the total weight of thefeedstock.

In an aspect, the feedstock can comprise C₁₃ and C₁₄ internalmonoolefins. Any feedstock comprising C₁₃ and C₁₄ internal monoolefinsof the type described herein can be used, for example a feedstockobtained from a commercial petroleum refining or petrochemical process.Such feedstocks can comprise other olefins in addition to the C₁₃ andC₁₄ internal monoolefins of the type described herein, for example C¹²⁻monoolefins, as well as C₁₅₊ monoolefins. An example of a C₁₃ and C₁₄internal monoolefins feedstock suitable for use in the presentdisclosure include NEODENE 1314 IO higher olefins (also known as NEODENE134 IO higher olefins), which contains a combination of C₁₃ and C₁₄internal olefins that is commercially available from Shell Chemicals. Atypical composition of NEODENE 1314 IO higher olefins is given in thetable below:

Component of NEODENE 1314 IO Unit Value Method C₁₂ & Lower (C₁₂₋) % m/m<2.0 SMS* 2976 [% mass/mass] C₁₃ % m/m 43-55 SMS 2976 C₁₄ % m/m 45-55SMS 2976 C₁₅ & Higher (C₁₅₋) % m/m <2.5 SMS 2976 Appearance Clear andVisual substantially free of visual impurities Color, Pt•Co <10 ASTMD1209- 05(2011) Water mg/kg <100 ASTM E1064-16 *SMS = Shell ModifiedSpot Test.

In an aspect, the feedstock can comprise at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, alternatively at least about 85 wt. %, alternatively at leastabout 90 wt. %, or alternatively at least about 95 wt. % C₁₃ and C₁₄internal monoolefins, based on the total weight of the feedstock. Insuch aspect, the feedstock can comprise (a) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2 wt. % C¹²⁻ monoolefins; and (b) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2.5 wt. % C₁₅₊ monoolefins; based on the total weight of the feedstock.For purposes of the disclosure herein, a feedstock comprising at leastabout 70 wt. % C₁₃ and C₁₄ internal monoolefins, based on the totalweight of the feedstock, can also be referred to as a “first C₁₃ and C₁₄feedstock.”

In another aspect, the feedstock can comprise at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % C₁₃ and C₁₄ internal monoolefins, based on the totalweight of the feedstock. For purposes of the disclosure herein, afeedstock comprising at least about 95 wt. % C₁₃ and C₁₄ internalmonoolefins, based on the total weight of the feedstock, can also bereferred to as a “second C₁₃ and C₁₄ feedstock.” In an aspect, thesecond C₁₃ and C₁₄ feedstock can be produced by purifying the first C₁₃and C₁₄ feedstock, such as for example by distillation of the first C₁₃and C₁₄ feedstock.

In some aspects, the C₁₃ internal monoolefins and C₁₄ internalmonoolefins of any feedstock described herein (e.g., a first C₁₃ and C₁₄feedstock or a second C₁₃ and C₁₄ feedstock) can comprise linear C₁₃internal monoolefins and linear C₁₄ internal monoolefins, respectively.

In other aspects, the C₁₃ internal monoolefins and C₁₄ internalmonoolefins of any feedstock described herein (e.g., a first C₁₃ and C₁₄feedstock or a second C₁₃ and C₁₄ feedstock) can comprise branched C₁₃internal monoolefins and branched C₁₄ internal monoolefins,respectively. The branched C₁₃ internal monoolefins can comprise methylbranches. The branched C₁₄ internal monoolefins can comprise methylbranches.

In yet other aspects, the C₁₃ and C₁₄ internal monoolefins can compriselinear C₁₃ internal monoolefins, linear C₁₄ internal monoolefins,branched C₁₃ internal monoolefins, branched C₁₄ internal monoolefins, orcombinations thereof.

In some aspects, the feedstock can comprise (A) at least about 35 wt. %,alternatively at least about 40 wt. %, or alternatively at least about45 wt. % C₁₃ internal monoolefins, and (B) at least about 35 wt. %,alternatively at least about 40 wt. %, alternatively at least about 45wt. % C₁₄ internal monoolefins; based on the total weight of thefeedstock.

In an aspect, the feedstock can comprise C₁₄ and C₁₆ alpha monoolefins,such as C₁₄ and C₁₆ linear alpha monoolefins. For purposes of thedisclosure herein, the terms “alpha olefin (monoolefin)” and “terminalolefin (monoolefin)” can be used interchangeably. Any feedstockcomprising C₁₄ and C₁₆ alpha monoolefins of the type described hereincan be used, for example a feedstock obtained from a commercialpetroleum refining or petrochemical process. Such feedstocks cancomprise other olefins in addition to the C₁₄ and C₁₆ alpha monoolefinsof the type described herein, for example C¹³⁻ monoolefins, as well asC₁₇₊ monoolefins. In some aspects, a feedstock comprising C₁₄ and C₁₆alpha monoolefins can further comprise C₁₅ monoolefins, such as C₁₅alpha monoolefin, C₁₅ linear alpha monoolefin, etc.

As will be appreciated by one of skill in the art, and with the help ofthis disclosure, a feedstock comprising linear olefins (e.g., linearalpha monoolefins, C₁₄ and C₁₆ linear alpha monoolefins) can furthercomprise a minor amount of branched monoolefins; or alternatively canexclude branched monoolefins. In some aspects, the feedstock comprisingC₁₄ and C₁₆ linear alpha monoolefins comprises less than 1 wt. %,alternatively less than 0.1 wt. %, alternatively less than 0.01 wt. %,alternatively less than 0.001 wt. %, or alternatively less than 0.0001wt. % branched monoolefins, based on the total weight of the feedstock.In an aspect, the feedstock comprising C₁₄ and C₁₆ linear alphamonoolefins is substantially free of branched monoolefins.

An example of a C₁₄ and C₁₆ alpha monoolefins feedstock suitable for usein the present disclosure include NEODENE 14/16 higher olefins, whichcontains a combination of C₁₄ and C₁₆ alpha olefins (2:1 blend of a highpurity 1-tetradecene (C₁₄) and 1-hexadecene (C₁₆) made by the ShellHigher Olefins Process (SHOP) by the oligomerisation of ethylene) thatis commercially available from Shell Chemicals. A typical composition ofNEODENE 14/16 higher olefins is given in the table below:

Component of NEODENE 14/16 Unit Value Method C₁₂ and lower (C₁₂₋) % m/m<2 SMS* 2895 [% mass/mass] C₁₄ % m/m 60-70 SMS 2895 C₁₆ % m/m 29-40 SMS2895 C₁₈ and higher (C₁₈₊) % m/m <2 SMS 2895 Total n-Alpha Olefins %m/m >92.5 SMS 2895 Total Branched Olefins % m/m <4.5 SMS 2895 TotalInternal Olefins % m/m <2.5 SMS 2895 Paraffin % m/m <0.2 SMS 2895Appearance Clear and Visual substantially free of visual impuritiesColor, Pt•Co <5 ASTM D1209- 05(2011) Water mg/kg <100 ASTM E1064-16Carbonyls as C═O mg/kg <15 SMS 2894 Peroxides as O mg/kg <3 SMS 359 *SMS= Shell Modified Spot Test.

In an aspect, the feedstock can comprise at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, alternatively at least about 85 wt. %, alternatively at leastabout 90 wt. %, or alternatively at least about 95 wt. % C₁₄ and C₁₆linear alpha monoolefins, based on the total weight of the feedstock. Insuch aspect, the feedstock can comprise (a) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2 wt. % C¹²⁻ monoolefins; and (b) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2 wt. % C₁₈₊ monoolefins; based on the total weight of the feedstock.For purposes of the disclosure herein, a feedstock comprising at leastabout 70 wt. % C₁₄ and C₁₆ linear alpha monoolefins, based on the totalweight of the feedstock, can also be referred to as a “first C₁₄ and C₁₆feedstock.”

In another aspect, the feedstock can comprise at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % C₁₄ and C₁₆ linear alpha monoolefins, based on the totalweight of the feedstock. For purposes of the disclosure herein, afeedstock comprising at least about 95 wt. % C₁₄ and C₁₆ linear alphamonoolefins, based on the total weight of the feedstock, can also bereferred to as a “second C₁₄ and C₁₆ feedstock.” In an aspect, thesecond C₁₄ and C₁₆ feedstock can be produced by purifying the first C₁₄and C₁₆ feedstock, such as for example by distillation of the first C₁₄and C₁₆ feedstock.

The feedstock comprising C₁₄ and C₁₆ linear alpha monoolefin (e.g., afirst C₁₄ and C₁₆ feedstock or a second C₁₄ and C₁₆ feedstock) cancomprise less than less than about 10 wt. %, alternatively less thanabout 7.5 wt. %, or alternatively less than about 4.5 wt. % branchedolefins, based on the total weight of the feedstock.

In some aspects, the feedstock can comprise (A) at least about 50 wt. %,alternatively at least about 55 wt. %, or alternatively at least about60 wt. % 1-tetradecene, and (B) at least about 20 wt. %, alternativelyat least about 25 wt. %, alternatively at least about 30 wt. %1-hexadecene, based on the total weight of the feedstock.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₁ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ andC₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) canbe reacted using a sulfur source to olefin molar ratio of from about 1:1to about 20:1, alternatively from about 2:1 to about 15:1, oralternatively from about 3:1 to about 10:1; as previously describedherein for the branched C₁₀ monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₁ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ andC₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) canbe reacted at a pressure of from about 30 psig (206 kPag) to about 1,500psig (10,300 kPag), alternatively from about 100 psig (690 kPag) toabout 1,250 psig (8,600 kPag), or alternatively from about 250 psig(1,700 kPag) to about 1,000 psig (6,900 kPag); as previously describedherein for the branched C₁₀ monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)can be reacted (as previously described herein for the branched C₁₀monoolefins) to produce olefin conversion of equal to or greater thanabout 70%, alternatively equal to or greater than about 75%, oralternatively equal to or greater than about 80%, alternatively equal toor greater than about 85%, or alternatively equal to or greater thanabout 90%.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)can be reacted in the presence of an initiating agent to produce a C₁₁₊mercaptans crude composition; wherein the initiating agent comprisesultraviolet (UV) radiation; as previously described herein for thebranched C₁₀ monoolefins. In such aspect, the initiating agent canfurther comprise a phosphite promoter, a photoinitiator, a sulfurscavenger, an antioxidant, and the like, or combinations thereof.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ andC₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) canbe reacted in the presence of an initiating agent to produce a C₁₁₊mercaptans crude composition; wherein the initiating agent comprises aacid catalyst; as previously described herein for the branched C₁₀monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ andC₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) canbe reacted in the presence of an initiating agent to produce a C₁₁₊mercaptans crude composition; wherein the initiating agent comprises ahydrodesulfurization (HDS) catalyst; as previously described herein forthe branched C₁₀ monoolefins.

As noted previously, any suitable feedstocks comprising one or more C₁₁monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) can bereacted with a sulfur source (e.g., H₂S) in the presence of aninitiating agent to produce a C₁₁₊ mercaptans crude composition, and theC₁₁₊ mercaptans crude composition can be further refined (e.g.,distilled or otherwise separated into one or more fractions such aslights, intermediate, and heavies) to yield various compositionsdescribed herein. As described in more detail herein, the type and/oramounts of the constituent components that form the C₁₁₊ mercaptanscrude composition can vary depending upon the feedstock (e.g., theamount and types of olefins therein), the reaction conditions, thecatalysts employed, etc., and one skilled in the art can tailor the postreactor processing of the C₁₁₊ mercaptans crude composition to accountfor the specific compounds present in a given C₁₁₊ mercaptans crudecomposition to yield various desired products and compositions of thetypes described herein.

Upon completion of the reaction of a feedstock comprising one or moreC₁₁ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) with asulfur source (e.g., H₂S), a reactor effluent can be recovered from thereactor and H₂S removed therefrom to yield a C₁₁₊ mercaptans crudecomposition. The term “C₁₁₊ mercaptans crude composition” or “C₁₁₊mercaptans crude product” refers to an unrefined effluent streamrecovered from the reactor after removal of the sulfur source (e.g.,H₂S), and in particular to a sulfur source-free effluent stream that hasnot undergone any additional post-reactor processing such as flashing,distillation, or other separation techniques or processes to remove anycomponents from the effluent stream other than the initial removal ofthe sulfur source.

The C₁₁₊ mercaptans crude composition comprises C₁₁₊ mercaptans and C₂₂₊sulfides formed by the reaction of the sulfur source (e.g., H₂S) and theone or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins;C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alphamonoolefins), wherein the structures of these C₁₁₊ mercaptans and C₂₂₊sulfides are consistent with (e.g., derived from) the structures of thecorresponding C₁₁₊ monoolefins. For example, in aspects where the one ormore C₁₁₊ monoolefins comprise 1-tetradecene (H₂C═CH—(CH₂)₁₁—CH₃) and1-hexadecene (H₂C═CH—(CH₂)₁₃—CH₃), the resulting C₁₁₊ mercaptans (C₁₄mercaptans and C₁₆ mercaptans) can be characterized by the followingstructures that are consistent with (e.g., derived from) the structuresof the corresponding 1-tetradecene and 1-hexadecene:

and the resulting C₂₂₊ sulfides (C₂₈ sulfides, C₃₀ sulfides, and C₃₂sulfides) can be characterized by the following structures that areconsistent with (e.g., derived from) the structures of the corresponding1-tetradecene and 1-hexadecene:

-   -   H₃C—(CH₂)₁₃—S—(CH₂)₁₃—CH₃ (C₂₈ sulfide);    -   H₃C—(CH₂)₁₁—CH(CH₃)—S—CH(CH₃)—(CH₂)₁₁—CH₃ (C₂₈ sulfide);    -   H₃C—(CH₂)₁₁—CH(CH₃)—S—(CH₂)₁₃—CH₃ (C₂₈ sulfide);    -   H₃C—(CH₂)₁₃—S—(CH₂)₁₅—CH₃ (C₃₀ sulfide);    -   H₃C—(CH₂)₁₁—CH(CH₃)—S—CH(CH₃)—(CH₂)₁₃—CH₃ (C₃₀ sulfide);    -   H₃C—(CH₂)₁₃—CH(CH₃)—S—(CH₂)₁₃—CH₃ (C₃₀ sulfide);    -   H₃C—(CH₂)₁₁—CH(CH₃)—S—(CH₂)₁₅—CH₃ (C₃₀ sulfide);    -   H₃C—(CH₂)₁₅—S—(CH₂)₁₅—CH₃ (C₃₂ sulfide);    -   H₃C—(CH₂)₁₃—CH(CH₃)—S—CH(CH₃)—(CH₂)₁₃—CH₃ (C₃₂ sulfide);    -   H₃C—(CH₂)₁₃—CH(CH₃)—S—(CH₂)₁₅—CH₃ (C₃₂ sulfide); etc.

Generally, the C₁₁₊ mercaptans are characterized by structure R⁶—SH,wherein R⁶ is a functional group (e.g., alkyl group) derived from theone or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins;C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alphamonoolefins) disclosed herein.

Generally, the C₂₂₊ sulfides are characterized by structure R⁷—S—R⁸,wherein both R⁷ and R⁸ can each independently be a functional groupderived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein. R⁷ and R⁸ can be the same ordifferent, e.g., R⁷ and R⁸ can have the same structure; R⁷ and R⁸ canhave different structures; R⁷ and R⁸ can have the same chain length; R⁷and R⁸ can have different chain length; etc.

As will be appreciated by one of skill in the art, and with the help ofthis disclosure, in aspects where the one or more C₁₁₊ monoolefins(e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internalmonoolefins) contain methyl branches in their structure, the resultingC₁₁₊ mercaptans and C₂₂₊ sulfides would also contain methyl branchesconsistent with (e.g., derived from) the structures of the correspondingC₁₁₊ monoolefins.

In addition to C₁₁₊ mercaptans and C₂₂₊ sulfides, the C₁₁₊ mercaptanscrude composition can comprise a number of other compounds such asunreacted olefins, inert compounds (e.g., alkanes), C¹⁰⁻ mercaptans,C²¹⁻ sulfides, and other impurities. The constituent componentscontained within the C₁₁₊ mercaptans crude composition can varydepending upon the composition of the feedstock (e.g., an unpurifiedfeedstock as compared to a purified feedstock as described herein) aswell as reaction conditions, catalyst, etc. In various aspects, a C₁₁₊mercaptans crude composition can comprise light, intermediate, and heavyfractions as described herein.

In some aspects, the C₁₁₊ mercaptans crude composition can comprise lessthan about 10 wt. %, alternatively less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively at less than about3 wt. %, alternatively less than about 2 wt. %, or alternatively lessthan about 1 wt. % C₂₂₊ sulfides, based on the total weight of the crudecomposition, wherein the C₂₂₊ sulfides are characterized by structureR⁷—S—R⁸, wherein both R⁷ and R⁸ can each independently be a functionalgroup derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In an aspect, a process of the present disclosure can further compriserecovering a reaction product from the C₁₁₊ mercaptans crudecomposition; wherein the reaction product can comprises C₁₁₊ mercaptansand/or C₂₂₊ sulfides, wherein the C₁₁₊ mercaptans are characterized bystructure R⁶—SH, wherein R⁶ is a functional group (e.g., alkyl group)derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein; and wherein the C₂₂₊sulfides are characterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸can each independently be a functional group derived from the one ormore C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ andC₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)disclosed herein.

In an aspect, the reaction product can comprise a C₁₁₊ mercaptanscomposition (intermediate fraction), a C₂₂₊ sulfides composition (heavyfraction), a C₁₁₊ mercaptans/C₂₂₊ sulfides composition (intermediate andheavy fractions), or combinations thereof.

In an aspect, a C₁₁₊ mercaptans crude composition as disclosed hereincan be separated into two or more fractions (e.g., light fraction,intermediate fraction, heavy fraction, etc.) by any process or unitoperation known in the art. For example, a C₁₁₊ mercaptans crudecomposition can be processed (e.g., distilled) to remove a fraction oflight compounds. Alternatively, a C₁₁₊ mercaptans crude composition canbe processed to recover both a light fraction and an intermediatefraction (e.g., a rough cut), followed by further processing to obtainone or more fine cuts. Alternatively, a C₁₁₊ mercaptans crudecomposition can be processed to recover a heavy fraction (e.g., a C₂₂₊sulfide fraction). Alternatively, a C₁₁₊ mercaptans crude compositioncan be processed to separate out any combination of a light fraction, anintermediate fraction (e.g., comprising C₁₁₊ mercaptans), and a heavyfraction (e.g., comprising C₂₂₊ sulfides). Furthermore, a light,intermediate or heavy fraction (e.g., a rough cut) can be furtherprocessed or parsed to obtain one or more desired fine cuts (e.g., aC₁₁₊ mercaptan fraction). Alternatively, a C₁₁₊ mercaptans crudecomposition can be separated to produce a high-purity C₁₁₊ mercaptanstream and/or a high-purity C₂₂₊ sulfide stream (e.g., to obtain adesired fine cut or fraction such as a C₁₁₊ mercaptan fraction).Further, these separated streams can be blended in any combination ofratios to produce a mixture with specific concentrations of one of morecomponents (e.g., desired blend ratios of C₁₁₊ mercaptans and/or C₂₂₊sulfides, for example to aid in a particular end use). The unitoperations/processes used for these separations are known to one ofskill and the art and include, but are not limited to, distillation,fractionation, flashing, stripping, and absorption, and others. The unitoperation conditions, such as for example, temperature, pressure, flowrates, and others at which these unit operations produce one or more ofthe desired fractions can easily be determined by one of ordinary skillin the art.

In an aspect, a light fraction is removed from the C₁₁₊ mercaptans crudecomposition, for example by flashing, distillation, fractionation,stripping, absorption, etc.

In an aspect, the light fraction removed from the C₁₁₊ mercaptans crudecomposition can comprise at least about 90 wt. %, alternatively at leastabout 90 wt. %, alternatively at least about 95 wt. %, alternatively atleast about 96 wt. %, alternatively at least about 97 wt. %,alternatively at least about 98 wt. %, alternatively at least about 99wt. % C¹⁰⁻ compounds, based on the total weight of the light fraction.Nonlimiting examples of C¹⁰⁻ compounds include C¹⁰⁻ monoolefins (e.g.,unreacted C¹⁰⁻ monoolefins), C¹⁰⁻ mercaptans, C¹⁰⁻ alkanes, C¹⁰⁻alcohols, and the like, or combinations thereof. In an aspect, the lightfraction removed from the C₁₁₊ mercaptans crude composition can compriseless than about 10 wt. %, alternatively less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively at less than about3 wt. %, alternatively less than about 2 wt. %, or alternatively lessthan about 1 wt. % C₁₁₊ compounds, based on the total weight of thelight fraction.

Following removal of the lights (for example, via flashing) from theC₁₁₊ mercaptans crude composition, a combined intermediate and heavyfraction (i.e., C₁₁₊ compounds sometimes referred to as a kettle productin the Examples) can remain, and the combined intermediate and heavyfraction can be used “as is” or can be further processed, for exampleseparated or split into separate intermediate and heavy fractions (andsaid separate intermediate and heavy fractions can be subsequentlyrecombined in various blends and associated blend ratios), as describedin more detail herein. In an aspect, a combined intermediate and heavyfraction (i.e., C₁₁₊ compounds) formed by removal of the light fractionfrom the C₁₁₊ mercaptans crude composition can comprise less than about15 wt. %, alternatively less than about 10 wt. %, alternatively lessthan about 9 wt. %, alternatively less than about 8 wt. %, alternativelyless than about 7 wt. %, alternatively less than about 6 wt. %,alternatively less than about 5 wt. %, alternatively less than about 4wt. %, alternatively less than about 3 wt. %, alternatively less thanabout 2 wt. %, alternatively less than about 1 wt. % C¹⁰⁻ products,based on the total weight of the combined intermediate and heavyfraction (i.e., C₁₁₊ compounds).

In an aspect, a combined intermediate and heavy fraction (i.e., C₁₁₊compounds) recovered from the from the C₁₁₊ mercaptans crude compositioncan comprise (A) at least about 50 wt. %, alternatively at least about60 wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. % C₁₁₊mercaptans, based on the total weight of the combined fraction, whereinthe C₁₁₊ mercaptans are characterized by structure R⁶—SH, wherein R⁶ isa functional group (e.g., alkyl group) derived from the one or more C₁₁₊monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosedherein; and (B) less than about 20 wt. %, alternatively less than about15 wt. %, alternatively less than about 10 wt. %, or alternatively lessthan about 5 wt. % C₂₂₊ sulfides, based on the total weight of thecombined fraction, wherein the C₂₂₊ sulfides are characterized bystructure R⁷—S—R⁸, wherein both R⁷ and R⁸ can each independently be afunctional group derived from the one or more C₁₁₊ monoolefins (e.g.,C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internal monoolefins; orC₁₄ and C₁₆ linear alpha monoolefins) disclosed herein.

In an embodiment, the C₁₁₊ mercaptans crude composition can be flashedto remove a lights fraction as described herein to produce a combinedintermediate and heavy fraction (i.e., C₁₁₊ compounds) comprising: (A)from at least about 50 wt. % to at least about 99 wt. %, alternativelyfrom at least about 50 wt. % to at least about 95 wt. %, alternativelyfrom at least about 55 wt. % to at least about 85 wt. %, oralternatively from at least about 60 wt. % to at least about 80 wt. %C₁₁₊ mercaptans, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the C₁₁₊ mercaptans can be C₁₁₊mercaptans characterized by structure R⁶—SH, wherein R⁶ is a functionalgroup (e.g., alkyl group) derived from the one or more C₁₁₊ monoolefins(e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internalmonoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosed herein;and (B) from about 1 wt. % to about 20 wt. %, alternatively from about 5wt. % to about 20 wt. %, alternatively from about 7.5 wt. % to about17.5 wt. %, or alternatively from about 10 wt. % to about 15 wt. % C₂₂₊sulfides; wherein at least about 50 wt. %, alternatively at least about60 wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 75 wt. %, alternatively at least about 80 wt. %, or alternativelyat least about 85 wt. % of the C₂₂₊ sulfides can be C₂₂₊ sulfidescharacterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸ can eachindependently be a functional group derived from the one or more C₁₁₊monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosedherein.

In an aspect, the C₁₁₊ mercaptans crude composition can be flashed toremove a light fraction and subsequently further separated to produce anintermediate fraction and a heavy fraction (i.e., C₁₁₊ compounds). Theintermediate fraction and the heavy fractions recovered from the C₁₁₊mercaptans crude composition can then be optionally further processed(e.g., polished) and mixed in any appropriate ratio to produce blendedcompositions, as previously described herein for crude compositionsderived from branched C₁₀ monoolefins.

In an aspect, an intermediate fraction recovered from the C₁₁₊mercaptans crude composition can comprise at least about 25 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 75 wt. %, or alternatively at least about 85 wt. % C₁₁₊mercaptans, based on the total weight of the intermediate fraction,wherein the C₁₁₊ mercaptans are characterized by structure R⁶—SH,wherein R⁶ is a functional group (e.g., alkyl group) derived from theone or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins;C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alphamonoolefins) disclosed herein.

In an aspect, the heavy fraction recovered from the C₁₁₊ mercaptanscrude composition can comprise at least about 5, 10, 15, 20, 25, 30, 35,40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. %, C₂₂₊ sulfides, based onthe total weight of the heavy fraction, wherein the C₂₂₊ sulfides arecharacterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸ can eachindependently be a functional group derived from the one or more C₁₁₊monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosedherein.

In an aspect, a C₁₁₊ mercaptans composition can comprise C₁₁₊mercaptans, wherein at least a portion of the C₁₁₊ mercaptans arecharacterized by structure R⁶—SH, wherein R⁶ is a functional group(e.g., alkyl group) derived from the one or more C₁₁₊ monoolefins (e.g.,C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internal monoolefins; orC₁₄ and C₁₆ linear alpha monoolefins) disclosed herein. In an aspect,the C₁₁₊ mercaptans composition can comprise any suitable amount of C₁₁₊mercaptans as disclosed herein.

In some aspects, a C₁₁₊ mercaptans composition can comprise at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % C₁₁₊ mercaptans, basedon the total weight of the C₁₁ mercaptans composition; wherein at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 75 wt. %,alternatively at least about 80 wt. %, or alternatively at least 85 wt.% of the C₁₁₊ mercaptans can be C₁₁₊ mercaptans characterized bystructure R⁶—SH, wherein R⁶ is a functional group (e.g., alkyl group)derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In other aspects, a C₁₁₊ mercaptans composition can consist of orconsist essentially of C₁₁₊ mercaptans characterized by structure R⁶—SH,wherein R⁶ is a functional group (e.g., alkyl group) derived from theone or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins;C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alphamonoolefins) disclosed herein.

In yet other aspects, a C₁₁₊ mercaptans composition can comprise atleast about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % C₁₁₊ mercaptans characterized bystructure R⁶—SH, wherein R⁶ is a functional group (e.g., alkyl group)derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In an aspect, a C₂₂₊ sulfides composition can comprise C₂₂₊ sulfides,wherein at least a portion of the C₂₂₊ sulfides are characterized bystructure R⁷—S—R⁸, wherein both R⁷ and R⁸ can each independently be afunctional group derived from the one or more C₁₁₊ monoolefins (e.g.,C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internal monoolefins; orC₁₄ and C₁₆ linear alpha monoolefins) disclosed herein. In an aspect,the C₂₂₊ sulfides composition can comprise any suitable amount of C₂₂₊sulfides as disclosed herein.

In some aspects, a C₂₂₊ sulfides composition can comprise C₂₂₊ sulfides,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of the C₂₂₊sulfides can be C₂₂₊ sulfides characterized by structure R⁷—S—R⁸,wherein both R⁷ and R⁸ can each independently be a functional groupderived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In other aspects, a C₂₂₊ sulfides composition can consist of or consistessentially of C₂₂₊ sulfides characterized by structure R⁷—S—R⁸, whereinboth R⁷ and R⁸ can each independently be a functional group derived fromthe one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internalmonoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linearalpha monoolefins) disclosed herein.

In yet other aspects, a C₂₂₊ sulfides composition comprises at leastabout 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 95, or 99 wt. % C₂₂₊ sulfides characterized by structureR⁷—S—R⁸, wherein both R⁷ and R⁸ can each independently be a functionalgroup derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In an aspect, a C₁₁₊ mercaptans/C₂₂₊ sulfides composition can compriseone or more C₁₁₊ mercaptans and one or more C₂₂₊ sulfides of the typedisclosed herein. In an aspect, the C₁₁₊ mercaptans/C₂₂₊ sulfidescomposition can comprise any suitable amount of C₁₁ mercaptans, and anysuitable amount of C₂₂₊ sulfides.

In an aspect, a C₁₁₊ mercaptans/C₂₂₊ sulfides composition can comprise(A) at least about 1 wt. %, alternatively at least about 5 wt. %,alternatively at least about 10 wt. %, alternatively at least about 15wt. %, alternatively at least about 20 wt. %, alternatively at leastabout 25 wt. %, alternatively at least about 30 wt. %, alternatively atleast about 40 wt. %, alternatively at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 80 wt. %, alternatively at leastabout 90 wt. %, alternatively at least about 95 wt. %, or alternativelyat least about 99 wt. % C₁₁₊ mercaptans, based on the total weight ofthe C₁₁₊ mercaptans/C₂₂₊ sulfides composition, wherein at least aportion of the C₁₁₊ mercaptans can be C₁₁₊ mercaptans characterized bystructure R⁶—SH, wherein R⁶ is a functional group (e.g., alkyl group)derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein; and (B) at least about 1 wt.%, alternatively at least about 5 wt. %, alternatively at least about 10wt. %, alternatively at least about 15 wt. %, alternatively at leastabout 20 wt. %, alternatively at least about 25 wt. %, alternatively atleast about 30 wt. %, alternatively at least about 40 wt. %,alternatively at least about 50 wt. %, alternatively at least about 60wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. % C₂₂₊sulfides, based on the total weight of the C₁₁₊ mercaptans/C₂₂₊ sulfidescomposition, wherein at least a portion of the C₂₂₊ sulfides can be C₂₂₊sulfides characterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸ caneach independently be a functional group derived from the one or moreC₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosedherein.

In an aspect, a C₁₁₊ mercaptans/C₂₂₊ sulfides composition can compriseC₁₁ mercaptans represented by structure R⁶—SH and/or C₂₂₊ sulfidesrepresented by structure R⁷—S—R⁸ that are formed by reacting an olefinfeedstock comprising C₁₁₊ monoolefins with H₂S as disclosed herein,wherein the C₁₁₊ monoolefins present in the olefin feedstock provide thealkyl group represented by R⁶, R⁷, and R⁸. In such aspects, the R⁶ groupof the C₁₁₊ mercaptans and/or the R⁷ and R⁸ groups of the C₂₂₊ sulfidesare provided by or derived from the counterpart R⁶, R⁷, and R⁸ groupspresent in the C₁₁₊ monoolefins in the olefin feedstock.

The C₁₁₊ mercaptans compositions, C₂₂₊ sulfides compositions, and C₁₁₊mercaptans/C₂₂₊ sulfides compositions can be salable or otherwise usedfor a variety of end uses such as mining ore collector compositions andchain transfer agents.

In an aspect, the C₁₁₊ mercaptans as disclosed herein can be furtherconverted to multi-sulfur containing compounds, which could then be usedfor any suitable applications, such as adhesives, epoxy adhesives, chaintransfer agents, catalyst sulfurization, lubricants, mining collectors,etc. In some aspects, the C₁₁₊ mercaptans as disclosed herein can befurther converted to polysulfides, which could then be used for epoxyadhesives. In other aspects, the C₁₁₊ mercaptans as disclosed herein canbe further converted to trithiocarbonates, which could then be used aschain transfer agents.

In an aspect, a C₁₁₊ mercaptans composition and/or a C₁₁₊mercaptans/C₂₂₊ sulfides composition comprising equal to or greater thanabout 25 wt. % C₁₁₊ mercaptans as disclosed herein can advantageouslyhave an odor less unpleasant than an odor of an otherwise similarcomposition comprising equal to or greater than about 25 wt. % n-dodecylmercaptan and/or tert-dodecyl mercaptan, as perceived by equal to orgreater than about 51% of human subjects exposed to the odor of eachcomposition. Additional advantages of the C₁₁₊ mercaptans compositions,C₂₂₊ sulfides compositions, and C₁₁₊ mercaptans/C₂₂₊ sulfidescompositions and processes of producing same as disclosed herein can beapparent to one of skill in the art viewing this disclosure.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore branched C₁₀₊ monoolefins in the presence of an initiating agent,as previously described herein for the branched C₁₀ monoolefins, toproduce a crude composition (also referred to as a crude product);wherein the crude composition comprises branched C₁₀₊ mercaptans andbranched C₂₀₊ sulfides.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore branched C₁₀₊ monoolefins in the presence of an initiating agent,as previously described herein for the branched C₁₀ monoolefins, toproduce a branched C₁₀₊ mercaptans crude composition (also referred toas a branched C₁₀₊ mercaptans crude product); wherein the branched C₁₀₊monoolefins comprise C₁₀ to C₃₀ monoolefins, alternatively C₁₁ to C₃₀monoolefins, alternatively C₁₂ to C₃₀ monoolefins, alternatively C₁₄ toC₃₀ monoolefins, alternatively C₁₆ to C₂₈ monoolefins, or alternativelyC₁₈ to C₂₆ monoolefins; and wherein the branched C₁₀₊ mercaptans crudecomposition comprises branched C₁₀₊ mercaptans and branched C₂₀₊sulfides.

The sulfur source can be any sulfur source suitable to provide sulfurfor the conversion of olefins (e.g., branched C₁₀₊ monoolefins) tomercaptans (e.g., branched C₁₀₊ mercaptans) and sulfides (e.g., branchedC₂₀₊ sulfides). The sulfur source can comprise H₂S, thioacetic acid, andthe like, or combinations thereof. In some aspects, the sulfur sourcecan comprise H₂S, as previously described herein.

The branched C₁₀₊ mercaptans crude composition can be further processed,for example via distillation, as previously described herein for thebranched C₁₀ monoolefins, to yield one or more products (also referredto as distilled, purified, refined, finished, or final products)selected from the group consisting of mercaptan compositions (e.g., acomposition comprising one or more branched C₁₀₊ mercaptans), sulfidecompositions (e.g., a composition comprising one or more branched C₂₀₊sulfides); and compositions having both mercaptans (e.g., branched C₁₀₊mercaptans) and sulfides (e.g., branched C₂₀₊ sulfides), referred to asmercaptan/sulfide compositions.

In an aspect, a C₁₀₊ mercaptans composition comprises one or morebranched C₁₀₊ mercaptans, wherein the branched C₁₀₊ mercaptans compriseC₁₀ to C₃₀ mercaptans, alternatively C₁₁ to C₃₀ mercaptans,alternatively C₁₂ to C₃₀ mercaptans, alternatively C₁₄ to C₃₀mercaptans, alternatively C₁₆ to C₂₈ mercaptans, or alternatively C₁₈ toC₂₆ mercaptans.

In an aspect, a C₂₀₊ sulfides composition comprises one or more branchedC₂₀₊ sulfides represented by the structure R¹⁰—S—R¹¹, wherein R¹⁰ andR¹¹ are each independently a functional group derived from an olefin,wherein the olefin comprises a branched C₁₀₊ monoolefin as disclosedherein. The branched C₂₀₊ sulfides comprise C₂₀ to C₆₀ sulfides,alternatively C₂₁ to C₆₀ sulfides, alternatively C₂₂ to C₆₀ sulfides,alternatively C₂₄ to C₆₀ sulfides, alternatively C₂₈ to C₆₀ sulfides,alternatively C₃₂ to C₅₆ sulfides, or alternatively C₃₆ to C₅₂ sulfides.

In an aspect, a C₁₀₊ mercaptans/C₂₀₊ sulfides composition comprises (A)one or more branched C₁₀₊ mercaptans; and (B) one or more branched C₂₀₊sulfides represented by the structure R¹—S—R¹¹.

The C₁₀₊ mercaptans compositions, C₂₀₊ sulfides compositions, and C₁₀₊mercaptans/C₂₀₊ sulfides compositions can be salable or otherwise usedfor a variety of end uses such as mining ore collector compositions andchain transfer agents.

In an aspect, the compositions disclosed herein can be prepared by aprocess comprising reacting, in a reactor, a sulfur source (e.g., H₂S)and a feedstock comprising one or more branched C₁₀₊ monoolefins in thepresence of an initiating agent to produce a branched C₁₀₊ mercaptanscrude (reaction product) composition, wherein the branched C₁₀₊monoolefins comprise a branched C₁₀₊ monoolefin represented by StructureI-1, a branched C₁₀₊ monoolefin represented by Structure J-1, a branchedC₁₀₊ monoolefin represented by Structure K-1, a branched C₁₀₊ monoolefinrepresented by Structure L-1, or combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group. The R⁹ can be a linear C₁ to C₂₁ alkyl group or abranched C₁ to C₂₁ alkyl group. As will be appreciated by one of skillin the art, and with the help of this disclosure, the C₁₀₊ monoolefinscomprising the R⁹ alkyl group are branched monoolefins, regardless ofwhether R⁹ is linear or branched, owing to a branched sub-structure thatis linked to the R⁹ alkyl group, as it can be seen in Structures I-1,J-1, K-1, and L-1.

In some aspects, R⁹ can be selected from the group consisting of amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, an undecyl group, a dodecyl group, a tridecyl group, atetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecylgroup, an octadecyl group, a nonadecyl group, an eicosyl group, ahenicosyl group, and combinations thereof.

In aspects where R⁹ is a methyl group, the branched C₁₀₊ monoolefinscomprise one or more branched C₁₀ monoolefins, as previously disclosedherein. The branched C₁₀ monoolefins can comprise 5-methyl-1-nonene(represented by Structure I), 3-propyl-1-heptene (represented byStructure J), 4-ethyl-1-octene (represented by Structure K),2-butyl-1-hexene (represented by Structure L), or combinations thereof.

Any feedstock comprising one or more branched C₁₀₊ monoolefins of thetype described herein can be used, for example a feedstock obtained froma commercial petroleum refining or petrochemical process. Suchfeedstocks can comprise other olefins in addition to the one or morebranched C₁₀₊ monoolefins of the type described herein, for examplelinear C₁₀₊ monoolefins as well as olefins having less than 10 carbonatoms.

In an aspect, the feedstock can comprise one or more branched C₁₀ to C₃₀monoolefins. Any feedstock comprising branched C₁₀ to C₃₀ monoolefins ofthe type described herein can be used, for example a feedstock obtainedfrom a commercial petroleum refining or petrochemical process. Suchfeedstocks can comprise other olefins in addition to the branched C₁₀ toC₃₀ monoolefins of the type described herein, for example C⁹⁻monoolefins, C₃₁₊ monoolefins, as well as linear C₁₀ to C₃₀ monoolefins.

In an aspect, the feedstock can comprise at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, alternatively at least about 85 wt. %, alternatively at leastabout 90 wt. %, or alternatively at least about 95 wt. % branched C₁₀ toC₃₀ monoolefins, based on the total weight of the feedstock. In suchaspect, the feedstock can comprise (a) less than about 15 wt. %,alternatively less than about 10 wt. %, alternatively less than about 5wt. %, or alternatively less than about 1 wt. % C⁹⁻ monoolefins; and (b)less than about 15 wt. %, alternatively less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about1 wt. % C₃₁₊ monoolefins; based on the total weight of the feedstock.For purposes of the disclosure herein, a feedstock comprising at leastabout 70 wt. % branched C₁₀ to C₃₀ monoolefins, based on the totalweight of the feedstock, can also be referred to as a “first C₁₀ to C₃₀feedstock.”

In another aspect, the feedstock can comprise at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % branched C₁₀ to C₃₀ monoolefins, based on the totalweight of the feedstock. For purposes of the disclosure herein, afeedstock comprising at least about 95 wt. % branched C₁₀ to C₃₀monoolefins, based on the total weight of the feedstock, can also bereferred to as a “second C₁₀ to C₃₀ feedstock.” In an aspect, the secondC₁₀ to C₃₀ feedstock can be produced by purifying the first C₁₀ to C₃₀feedstock, such as for example by distillation of the first C₁₀ to C₃₀feedstock.

In an aspect, the C₁₀ to C₃₀ monoolefins of any feedstock describedherein (e.g., a first C₁₀ to C₃₀ feedstock or a second C₁₀ to C₃₀feedstock) can comprise, can consist essentially of, or can be, abranched C₁₀₊ monoolefin represented by Structure I-1, a branched C₁₀₊monoolefin represented by Structure J-1, a branched C₁₀₊ monoolefinrepresented by Structure K-1, and a branched C₁₀₊ monoolefin representedby Structure L-1; wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively aC₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkyl group,alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkylgroup, or alternatively a C₉ to C₁₇ alkyl group.

In an aspect, the C₁₀ to C₃₀ monoolefins of any feedstock describedherein (e.g., a first C₁₀ to C₃₀ feedstock or a second C₁₀ to C₃₀feedstock) can comprise linear C₁₀ to C₃₀ monoolefins. In an aspect, theC₁₀ to C₃₀ monoolefins of any feedstock described herein can compriseless than or equal to about 26 mol %, alternatively less than or equalto about 24 mol %, alternatively less than or equal to about 22 mol %,alternatively less than or equal to about 20 mol %, or alternativelyless than or equal to about 18 mol % linear C₁₀ to C₃₀ monoolefins. Insome aspects, the C₁₀ to C₃₀ monoolefins of any feedstock describedherein can comprise from about 0.1 mol % to about 26 mol %,alternatively from about 0.5 mol % to about 24 mol %, alternatively fromabout 1 mol % to about 22 mol %, alternatively from about 1.5 mol % toabout 20 mol %, or alternatively from about 2.5 mol % to about 18 mol %linear C₁₀ to C₃₀ monoolefins.

In an aspect, the first C₁₀ to C₃₀ feedstock disclosed herein canfurther comprise C⁹⁻ monoolefins, C₃₁₊ monoolefins, or combinationsthereof; alternatively, C⁹⁻ monoolefins; or alternatively, C₃₁₊monoolefins. In an aspect, the C⁹⁻ monoolefins can comprise, can consistessentially of, or can be, a C₇ monoolefin, a C₈ monoolefin, a C₉monoolefin, or combinations thereof; alternatively, a C₇ monoolefin;alternatively, a C₈ monoolefin; or alternatively, a C₉ monoolefin. Insome aspects, the C⁹⁻ monoolefins can comprise, can consist essentiallyof, or can be, a C₈ monoolefin. In an aspect, the C₃₁₊ monoolefins cancomprise, can consist essentially of, or can be, a C₃₁ monoolefin, a C₃₂monoolefin, a C₃₃ monoolefin, a C₃₄ monoolefin, a C₃₅ monoolefin, a C₃₆monoolefin, a C₃₇ monoolefin, a C₃₈ monoolefin, or combinations thereof;alternatively, a C₃₁ monoolefin; alternatively, a C₃₂ monoolefin;alternatively, a C₃₃ monoolefin; alternatively, a C₃₄ monoolefin;alternatively, a C₃₅ monoolefin; alternatively, a C₃₆ monoolefin;alternatively, a C₃₇ monoolefin; or alternatively, a C₃₈ monoolefin. Insome aspects, the C₃₁₊ monoolefins can comprise, can consist essentiallyof, or can be, a C₃₂ monoolefin, a C₃₆ monoolefin, a C₃₈ monoolefin, orcombinations thereof; alternatively, a C₃₂ monoolefin; alternatively, aC₃₆ monoolefin; or alternatively, a C₃₈ monoolefin.

In an aspect, the first C₁₀ to C₃₀ feedstock can further comprise fromabout 0.1 mol % to about 5 mol %, alternatively from about 0.25 mol % toabout 4 mol %, or alternatively from about 0.5 mol % to about 3 mol % C₈monoolefins. In such aspect, the C₈ monoolefins can comprise at leastabout 95 mol %, alternatively at least about 96 mol %, alternatively atleast about 97 mol %, alternatively at least about 98 mol %, oralternatively at least about 99 mol % 1-octene.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted using a sulfursource to olefin molar ratio of from about 1:1 to about 20:1,alternatively from about 2:1 to about 15:1, or alternatively from about3:1 to about 10:1; as previously described herein for the branched C₁₀monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted at a pressure offrom about 30 psig (206 kPag) to about 1,500 psig (10,300 kPag),alternatively from about 100 psig (690 kPag) to about 1,250 psig (8,600kPag), or alternatively from about 250 psig (1,700 kPag) to about 1,000psig (6,900 kPag); as previously described herein for the branched C₁₀monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted (as previouslydescribed herein for the branched C₁₀ monoolefins) to produce olefinconversion of equal to or greater than about 70%, alternatively equal toor greater than about 75%, or alternatively equal to or greater thanabout 80%, alternatively equal to or greater than about 85%, oralternatively equal to or greater than about 90%.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted in the presenceof an initiating agent to produce a branched C₁₀₊ mercaptans crudecomposition; wherein the initiating agent comprises ultraviolet (UV)radiation; as previously described herein for the branched C₁₀monoolefins. In such aspect, the initiating agent can further comprise aphosphite promoter, a photoinitiator, a sulfur scavenger, anantioxidant, and the like, or combinations thereof.

In an aspect, H₂S and a feedstock comprising one or more branched C₁₀ toC₃₀ monoolefins can be reacted in the presence of UV radiation at a H₂Sto olefin molar ratio of from about 1:1 to about 15:1, alternativelyfrom about 2:1 to about 12.5:1, or alternatively from about 5:1 to about10:1; as previously described herein for the branched C₁₀ monoolefins.

In an aspect, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ to C₃₀ monoolefins in the presenceof UV radiation to produce a branched C₁₀₊ mercaptans crude composition(wherein the branched C₁₀₊ mercaptans crude composition comprises from50-100 wt. % C₁₀ to C₃₀ mercaptans, alternatively from 50-90 wt. % C₁₀to C₃₀ mercaptans, or alternatively from 75-85 wt. % C₁₀ to C₃₀mercaptans); wherein the C₁₀ to C₃₀ mercaptans present in the crudecomposition further comprise from about 70 wt. % to about 100 wt. %,alternatively from about 70 wt. % to about 95 wt. %, alternatively fromabout 80 wt. % to about 90 wt. %, or alternatively from about 79 wt. %to about 85 wt. % C₁₀ to C₃₀ primary mercaptans; from about 0 wt. % toabout 30 wt. %, alternatively from about 0 wt. % to about 20 wt. %,alternatively from about 10 wt. % to about 20 wt. %, or alternativelyfrom about 5 wt. % to about 19 wt. % C₁₀ to C₃₀ secondary mercaptans;and from about 0 wt. % to about 10 wt. %, alternatively from about 0 wt.% to about 5 wt. %, or alternatively from about 0 wt. % to about 3 wt. %C₁₀ to C₃₀ tertiary mercaptans. As will be appreciated by one of skillin the art, and with the help of this disclosure, the make-up of thebranched C₁₀₊ mercaptans crude composition, in terms of primary,secondary, and tertiary mercaptans, will depend on the make-up of thefeedstock, as well as on the reaction conditions. Further, as will beappreciated by one of skill in the art, and with the help of thisdisclosure, the make-up of each of the primary, secondary, and tertiarymercaptans will depend on the make-up of the feedstock, as well as onthe reaction conditions.

In an aspect, the C₁₀ to C₃₀ primary mercaptans can comprise a branchedC₁₀₊ mercaptan represented by Structure A-1, a branched C₁₀₊ mercaptanrepresented by Structure B-1, a branched C₁₀₊ mercaptan represented byStructure C-1, a branched C₁₀₊ mercaptan represented by Structure D-1,or combinations thereof; wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

The C₁₀ to C₃₀ primary mercaptans can further comprise a linear C₁₀₊mercaptan represented by Structure M-1; wherein R⁹ is a C₁ to C₂₁ alkylgroup, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In aspects where R⁹ is a methyl group, the C₁₀ to C₃₀ primary mercaptanscomprise one or more branched primary C₁₀ mercaptans, as previouslydisclosed herein. The branched primary C₁₀ mercaptans can comprise5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D), or combinationsthereof. Primary C₁₀ mercaptans can further comprise 1-mercapto-decane(represented by Structure M), as disclosed herein.

In an aspect, the C₁₀ to C₃₀ secondary mercaptans can comprise abranched C₁₀₊ mercaptan represented by Structure E-1, a branched C₁₀₊mercaptan represented by Structure F-1, a branched C₁₀₊ mercaptanrepresented by Structure G-1, or combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

The C₁₀ to C₃₀ secondary mercaptans can further comprise a linear C₁₀₊mercaptan represented by Structure N-1, a linear C₁₀₊ mercaptanrepresented by Structure O-1, a linear C₁₀ mercaptan represented byStructure P-1, or combinations thereof; wherein R⁹ is a C₁ to C₂₁ alkylgroup, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In aspects where R⁹ is a methyl group, the C₁₀ to C₃₀ secondarymercaptans comprise one or more branched secondary C₁₀ mercaptans, aspreviously disclosed herein. The branched secondary C₁₀ mercaptans cancomprise 5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G), or combinationsthereof. Secondary C₁₀ mercaptans can further comprise 4-mercapto-decane(represented by Structure N), 5-mercapto-decane (represented byStructure O), 2-mercapto-decane (represented by Structure P), orcombinations thereof; as disclosed herein.

In an aspect, the C₁₀ to C₃₀ tertiary mercaptans can comprise equal toor greater than about 90 wt. %, alternatively equal to or greater thanabout 95 wt. %, or alternatively equal to or greater than about 99 wt. %of a branched C₁₀₊ mercaptan represented by Structure H-1; wherein R⁹ isa C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In aspects where R⁹ is a methyl group, the C₁₀ to C₃₀ tertiarymercaptans comprise one or more branched tertiary C₁₀ mercaptans, aspreviously disclosed herein. The branched tertiary C₁₀ mercaptans cancomprise 5-methyl-5-mercapto-nonane (represented by Structure H), asdisclosed herein.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted in the presenceof an initiating agent to produce a branched C₁₀₊ mercaptans crudecomposition; wherein the initiating agent comprises an acid catalyst; aspreviously described herein for the branched C₁₀ monoolefins.

In an aspect, H₂S and a feedstock comprising one or more branched C₁₀ toC₃₀ monoolefins can be reacted in the presence of an acid catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1; as previously described herein for the branched C₁₀monoolefins.

In an aspect, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ to C₃₀ monoolefins in the presenceof an acid catalyst to produce a branched C₁₀₊ mercaptans crudecomposition (wherein the branched C₁₀₊ mercaptans crude compositioncomprises from 50-100 wt. % C₁₀ to C₃₀ mercaptans, alternatively from50-90 wt. % C₁₀ to C₃₀ mercaptans, or alternatively from 75-85 wt. % C₁₀to C₃₀ mercaptans); wherein the C₁₀ to C₃₀ mercaptans comprise fromabout 0 wt. % to about 5 wt. % alternatively from about 0.1 wt. % toabout 4 wt. %, or alternatively from about 0.5 wt. % to about 2.5 wt. %C₁₀ to C₃₀ primary mercaptans; from about 80 wt. % to about 95 wt. %,alternatively from about 82.5 wt. % to about 92.5 wt. %, oralternatively from about 85 wt. % to about 90 wt. % C₁₀ to C₃₀ secondarymercaptans; and from about 5 wt. % to about 20 wt. %, alternatively fromabout 7.5 wt. % to about 17.5 wt. %, or alternatively from about 10 wt.% to about 15 wt. % C₁₀ to C₃₀ tertiary mercaptans.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted in the presenceof an initiating agent to produce a branched C₁₀₊ mercaptans crudecomposition; wherein the initiating agent comprises ahydrodesulfurization (HDS) catalyst; as previously described herein forthe branched C₁₀ monoolefins.

In an aspect, H₂S and a feedstock comprising one or more branched C₁₀ toC₃₀ monoolefins can be reacted in the presence of an HDS catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1; as previously described herein for the branched C₁₀monoolefins.

In an aspect, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ to C₃₀ monoolefins in the presenceof an HDS catalyst to produce a branched C₁₀₊ mercaptans crudecomposition (wherein the branched C₁₀₊ mercaptans crude compositioncomprises from 50-100 wt. % C₁₀ to C₃₀ mercaptans, alternatively from50-90 wt. % C₁₀ to C₃₀ mercaptans, or alternatively from 75-85 wt. % C₁₀to C₃₀ mercaptans); wherein the C₁₀ to C₃₀ mercaptans comprise fromabout 5 wt. % to about 30 wt. % alternatively from about 10 wt. % toabout 25 wt. %, or alternatively from about 15 wt. % to about 20 wt. %C₁₀ to C₃₀ primary mercaptans; from about 60 wt. % to about 75 wt. %,alternatively from about 62.5 wt. % to about 72.5 wt. %, oralternatively from about 65 wt. % to about 70 wt. % C₁₀ to C₃₀ secondarymercaptans; and from about 5 wt. % to about 15 wt. %, alternatively fromabout 7.5 wt. % to about 13.5 wt. %, or alternatively from about 9 wt. %to about 12 wt. % C₁₀ to C₃₀ tertiary mercaptans.

As noted previously, any suitable feedstocks comprising one or morebranched C₁₀ to C₃₀ monoolefins can be reacted with a sulfur source(e.g., H₂S) in the presence of an initiating agent to produce a branchedC₁₀₊ mercaptans crude composition, and the branched C₁₀₊ mercaptanscrude composition can be further refined (e.g., distilled or otherwiseseparated into one or more fractions such as lights, intermediate, andheavies) to yield various compositions described herein. As described inmore detail herein, the type and/or amounts of the constituentcomponents that form the branched C₁₀₊ mercaptans crude composition canvary depending upon the feedstock (e.g., the amount and types of olefinstherein), the reaction conditions, the catalysts employed, etc., and oneskilled in the art can tailor the post reactor processing of thebranched C₁₀₊ mercaptans crude composition to account for the specificcompounds present in a given branched C₁₀₊ mercaptans crude compositionto yield various desired products and compositions of the typesdescribed herein.

Upon completion of the reaction of a feedstock comprising one or morebranched C₁₀ to C₃₀ monoolefins with a sulfur source (e.g., H₂S), areactor effluent can be recovered from the reactor and sulfur source(e.g., H₂S) removed therefrom to yield a branched C₁₀₊ mercaptans crudecomposition; as previously described herein for the branched C₁₀monoolefins. The term “branched C₁₀₊ mercaptans crude composition” or“branched C₁₀₊ mercaptans crude product” refers to an unrefined effluentstream recovered from the reactor after removal of the sulfur source(e.g., H₂S), and in particular to a sulfur source-free effluent streamthat has not undergone any additional post-reactor processing such asflashing, distillation, or other separation techniques or processes toremove any components from the effluent stream other than the initialremoval of the sulfur source.

The branched C₁₀₊ mercaptans crude composition comprises branched C₁₀ toC₃₀ mercaptans and branched C₂₀ to C₆₀ sulfides formed by the reactionof H₂S and the one or more branched C₁₀ to C₃₀ monoolefins, and thestructures of these branched C₁₀ to C₃₀ mercaptans and branched C₂₀ toC₆₀ sulfides are described in more detail herein. In addition tobranched C₁₀ to C₃₀ mercaptans and branched C₂₀ to C₆₀ sulfides, thebranched C₁₀₊ mercaptans crude composition can comprise a number ofother compounds such as unreacted olefins, inert compounds (e.g.,alkanes), non-branched C₁₀ to C₃₀ mercaptans, non-branched C₂₀ to C₆₀sulfides, non-C₁₀ to C₃₀ mercaptans (e.g., C⁹⁻ mercaptans), non-C₂₀ toC₆₀ sulfides (e.g., C¹⁹⁻ sulfides), and other impurities. Theconstituent components contained within the branched C₁₀₊ mercaptanscrude composition can vary depending upon the composition of thefeedstock (e.g., an unpurified first C₁₀ to C₃₀ feedstock as compared toa purified second C₁₀ to C₃₀ feedstock as described herein) as well asreaction conditions, catalyst, etc. In various aspects, a branched C₁₀₊mercaptans crude composition can comprise light, intermediate, and heavyfractions as described herein.

In an aspect, the branched C₁₀₊ mercaptans crude composition can containa variety of other non-C₁₀ to C₃₀ mercaptans and non-C₂₀ to C₆₀ sulfidescomponents (e.g., impurities) such as C₈ mercaptans; C₁₆ to C₁₉ sulfidesrepresented by the structure R¹²—S—R¹³, wherein R¹² and R¹³ are eachindependently a functional group derived from a C₈₊ monoolefin, whereinR¹² and R¹³ are not both derived from a branched C₁₀₊ monoolefin;unreacted C₈₊ monoolefins; non-olefin impurities selected from the groupconsisting of C₈₋₁₄ alkanes, cyclohexane, methylcyclopentane,methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene,hexamethylbenzene, C₄₋₁₂ alcohols, 2-ethyl-1-hexanol, and2-ethylhexyl-2-ethylhexanoate; and combinations thereof.

In an aspect, a process of the present disclosure can further compriserecovering a reaction product from the branched C₁₀₊ mercaptans crudecomposition; wherein the reaction product can comprise branched C₁₀₊mercaptans and/or branched C₂₀₊ sulfides, wherein the branched C₁₀₊mercaptans comprise branched C₁₀ to C₃₀ mercaptans; and wherein thebranched C₂₀₊ sulfides comprise branched C₂₀ to C₆₀ sulfides representedby the structure R¹⁰—SR¹¹, wherein R¹⁰ and R¹¹ are each independently afunctional group derived from an olefin, wherein the olefin comprises abranched C₁₀₊ monoolefin as disclosed herein.

In an aspect, the reaction product can comprise a branched C₁₀₊mercaptans composition (intermediate fraction; first reaction product),a branched C₂₀₊ sulfides composition (heavy fraction; second reactionproduct), a branched C₁₀₊ mercaptans/branched C₂₀₊ sulfides composition(intermediate and heavy fractions; first and second reaction products),or combinations thereof.

In an aspect, a branched C₁₀₊ mercaptans crude composition comprisingbranched C₁₀₊ mercaptans and branched C₂₀₊ sulfides as disclosed hereincan be separated into two or more fractions (e.g., light fraction,intermediate fraction, heavy fraction, etc.) by any process or unitoperation known in the art. For example, a branched C₁₀₊ mercaptanscrude composition can be processed (e.g., distilled) to remove afraction of light compounds. Alternatively, a branched C₁₀₊ mercaptanscrude composition can be processed to recover both a light fraction andan intermediate fraction (e.g., a rough cut), followed by furtherprocessing to obtain one or more fine cuts. Alternatively, a branchedC₁₀₊ mercaptans crude composition can be processed to recover a heavyfraction (e.g., a C₂₀₊ sulfides fraction). Alternatively, a branchedC₁₀₊ mercaptans crude composition can be processed to separate out anycombination of a light fraction, an intermediate fraction (e.g.,comprising C₁₀₊ mercaptans, including branched C₁₀₊ mercaptans), and aheavy fraction (e.g., comprising C₂₀₊ sulfides, including branched C₂₀₊sulfides). Furthermore, a light, intermediate or heavy fraction (e.g., arough cut) can be further processed or parsed to obtain one or moredesired fine cuts (e.g., a C₁₀ to C₃₀ mercaptan fraction).Alternatively, a branched C₁₀₊ mercaptans crude composition can beseparated to produce a high-purity C₁₀₊ mercaptan stream and/or ahigh-purity C₂₀₊ sulfide stream (e.g., to obtain a desired fine cut orfraction such as a C₁₀ to C₃₀ mercaptan fraction). Further, theseseparated streams can be blended in any combination of ratios to producea mixture with specific concentrations of one of more components (e.g.,desired blend ratios of branched C₁₀₊ mercaptans and/or branched C₂₀₊sulfides, for example to aid in a particular end use). The unitoperations/processes used for these separations are known to one ofskill and the art and include, but are not limited to, distillation,fractionation, flashing, stripping, and absorption, and others. The unitoperation conditions, such as for example, temperature, pressure, flowrates, and others at which these unit operations produce one or more ofthe desired fractions can easily be determined by one of ordinary skillin the art.

In an aspect, a light fraction is removed from the branched C₁₀₊mercaptans crude composition, for example by flashing, distillation,fractionation, stripping, absorption, etc.

In an aspect, the light fraction removed from the branched C₁₀₊mercaptans crude composition can comprise at least about 90 wt. %,alternatively at least about 92 wt. %, alternatively at least about 95wt. %, alternatively at least about 96 wt. %, alternatively at leastabout 97 wt. %, alternatively at least about 98 wt. %, alternatively atleast about 99 wt. % C⁹⁻ compounds, based on the total weight of thelight fraction. Nonlimiting examples of C⁹⁻ compounds include C⁹⁻monoolefins (e.g., unreacted C⁹⁻ monoolefins), C⁹⁻ mercaptans, C⁹⁻alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene,toluene, ethylbenzene, xylene, mesitylene, C⁹⁻ alcohols,2-ethyl-1-hexanol, and the like, or combinations thereof. In an aspect,the light fraction removed from the branched C₁₀₊ mercaptans crudecomposition can comprise less than about 10 wt. %, alternatively lessthan about 5 wt. %, alternatively less than about 4 wt. %, alternativelyat less than about 3 wt. %, alternatively less than about 2 wt. %,alternatively less than about 1 wt. % C₁₀₊ compounds, based on the totalweight of the light fraction.

Following removal of the lights (for example, via flashing) from thebranched C₁₀₊ mercaptans crude composition, a combined intermediate andheavy fraction (i.e., C₁₀₊ compounds sometimes referred to as a kettleproduct in the Examples) can remain, and the combined intermediate andheavy fraction can be used “as is” or can be further processed, forexample separated or split into separate intermediate and heavyfractions (and said separate intermediate and heavy fractions can besubsequently recombined in various blends and associated blend ratios),as described in more detail herein. In an aspect, a combinedintermediate and heavy fraction (i.e., C₁₀₊ compounds) formed by removalof the light fraction from the branched C₁₀₊ mercaptans crudecomposition can comprise less than about 15 wt. %, alternatively lessthan about 10 wt. %, alternatively less than about 9 wt. %,alternatively less than about 8 wt. %, alternatively less than about 7wt. %, alternatively less than about 6 wt. %, alternatively less thanabout 5 wt. %, alternatively less than about 4 wt. %, alternatively lessthan about 3 wt. %, alternatively less than about 2 wt. %, oralternatively less than about 1 wt. % C⁹⁻ products, based on the totalweight of the combined intermediate and heavy fraction (i.e., C₁₀₊compounds).

In an aspect, a combined intermediate and heavy fraction (i.e., C₁₀₊compounds) recovered from the branched C₁₀₊ mercaptans crude compositioncan comprise (A) at least about 50 wt. %, alternatively at least about60 wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. %mercaptans, based on the total weight of the combined fraction; whereinat least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the mercaptans can be branched C₁₀ to C₃₀ mercaptansselected from the group consisting of a branched C₁₀ to C₃₀ mercaptanrepresented by Structure A-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure B-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and (B) at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, alternatively at least about 25 wt. % sulfides, oralternatively at least about 30 wt. % sulfides; wherein at least about50 wt. %, alternatively at least about 60 wt. %, alternatively at leastabout 70 wt. %, alternatively at least about 75 wt. %, alternatively atleast about 80 wt. %, or alternatively at least about 85 wt. % of thesulfides can be branched C₂₀ to C₆₀ sulfides represented by structureR¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently be afunctional group derived from an olefin, wherein the olefin comprises abranched C₁₀ to C₃₀ monoolefin represented by Structure I-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure J-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof; andwherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkylgroup, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁alkyl group, alternatively a C₇ to C₁₉ alkyl group, or alternatively aC₉ to C₁₇ alkyl group.

In an aspect, the branched C₁₀₊ mercaptans crude composition can beflashed to remove a light fraction as described herein to produce acombined intermediate and heavy fraction (i.e., C₁₀₊ compounds)comprising: (A) at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, or 85 wt. % C₁₀₊ branched mercaptans selected from the groupconsisting of a branched C₁₀ to C₃₀ mercaptan represented by StructureA-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure B-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure C-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure D-1, a branched C₁₀ to C₃₀mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and (B) at leastabout 5 wt. %, alternatively at least about 10 wt. %, alternatively atleast about 15 wt. %, alternatively at least about 20 wt. %,alternatively at least about 25 wt. %, or alternatively at least about30 wt. % branched C₂₀ to C₆₀ sulfides represented by structureR¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently be afunctional group derived from an olefin, wherein the olefin comprises abranched C₁₀ to C₃₀ monoolefin represented by Structure I-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure J-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof; andwherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkylgroup, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁alkyl group, alternatively a C₇ to C₁₉ alkyl group, or alternatively aC₉ to C₁₇ alkyl group.

In an aspect, the branched C₁₀₊ mercaptans crude composition can beflashed to remove a lights fraction as described herein to produce acombined intermediate and heavy fraction (i.e., C₁₀₊ compounds)comprising: (A) from at least about 50 wt. % to at least about 90 wt. %,alternatively from at least about 55 wt. % to at least about 85 wt. %,or alternatively from at least about 60 wt. % to at least about 80 wt. %mercaptans, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the mercaptans can be branchedC₁₀ to C₃₀ mercaptans selected from the group consisting of a branchedC₁₀ to C₃₀ mercaptan represented by Structure A-1, a branched C₁₀ to C₃₀mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and (B) from atleast about 10 wt. % to at least about 30 wt. %, alternatively from atleast about 10 wt. % to at least about 25 wt. %, alternatively from atleast about 12.5 wt. % to at least about 22.5 wt. %, or alternativelyfrom at least about 15 wt. % to at least about 20 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ to C₆₀ sulfidesrepresented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can eachindependently be a functional group derived from an olefin, wherein theolefin comprises a branched C₁₀ to C₃₀ monoolefin represented byStructure I-1, a branched C₁₀ to C₃₀ monoolefin represented by StructureJ-1, a branched C₁₀ to C₃₀ monoolefin represented by Structure K-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure L-1, orcombinations thereof; and wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In an aspect, the branched C₁₀₊ mercaptans crude composition can beflashed to remove a light fraction and subsequently further separated toproduce an intermediate fraction and a heavy fraction (i.e., C₁₀₊compounds). The intermediate fraction and the heavy fractions recoveredfrom the branched C₁₀₊ mercaptans crude composition can then beoptionally further processed (e.g., polished) and mixed in anyappropriate ratio to produce blended compositions, as previouslydescribed herein for crude compositions derived from branched C₁₀monoolefins.

In an aspect, an intermediate fraction recovered from the branched C₁₀₊mercaptans crude composition can comprise at least about 25 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 75 wt. %, or alternatively at least about 85 wt. % C₁₀₊mercaptans, based on the total weight of the intermediate fraction,wherein the C₁₀₊ mercaptans are branched C₁₀ to C₃₀ mercaptans asdisclosed herein.

In an aspect, the heavy fraction recovered from the branched C₁₀₊mercaptans crude composition can comprise at least about 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. %, C₂₀₊sulfides, based on the total weight of the heavy fraction, wherein theC₂₀₊ sulfides are branched C₂₀ to C₆₀ sulfides as disclosed herein.

In an aspect, the branched C₁₀₊ mercaptans crude composition can beseparated into light, intermediate, and heavy fractions by distillation,for example in a single distillation column having a light fractionrecovered as an overhead stream, an intermediate fraction (e.g.,comprising C₁₀₊ compounds, including branched C₁₀₊ mercaptans) recoveredas a side stream, and a heavy fraction (e.g., comprising C₂₀₊ compounds,including branched C₂₀₊ sulfides) recovered as a bottom stream. Inalternative aspects, the separation can be in sequential steps such asremoval of the lights fraction in a first distillation column, followedby separation of the intermediate fraction (e.g., comprising C₁₀₊compounds, including branched C₁₀₊ mercaptans) as an overhead stream ina second distillation column and the heavy fraction (e.g., comprisingC₂₀₊ compounds, including branched C₂₀₊ sulfides) as a bottom stream ofthe second distillation column. These “rough-cut” light, intermediate,and heavy streams can be used “as is” or they can be further processed(e.g., further refined or polished, for example by additionaldistillation or other separation techniques to produce “fine-cuts”)and/or blended to obtain a variety of products that are salable orotherwise available for a variety of end uses such as mining orecollector compositions or chain transfer agents. For example, a varietyof C₁₀₊ mercaptans compositions, C₂₀₊ sulfides compositions, and mixedC₁₀₊ mercaptans/C₂₀₊ sulfides compositions can be produced of the typedisclosed in more detail herein.

In aspects where the olefin feedstock (e.g., olefin feedstock reactedwith a sulfur source (e.g., H₂S) in the presence of an initiating agentto produce the branched C₁₀₊ mercaptans crude composition) comprises C₁₀to C₁₉ monoolefins, the intermediate fraction comprises C₁₀ to C₁₉mercaptans, and the heavy fraction comprises C₂₀ to C₃₈ sulfides.

In aspects where the olefin feedstock (e.g., olefin feedstock reactedwith a sulfur source (e.g., H₂S) in the presence of an initiating agentto produce the branched C₁₀₊ mercaptans crude composition) comprises C₂₀to C₃₀ monoolefins, the intermediate fraction comprises C₂₀ to C₃₀mercaptans, and the heavy fraction comprises C₄₀ to C₆₀ sulfides.

In aspects where the olefin feedstock (e.g., olefin feedstock reactedwith a sulfur source (e.g., H₂S) in the presence of an initiating agentto produce the branched C₁₀₊ mercaptans crude composition) comprises C₁₀to C₃₀ monoolefins, the intermediate and heavy fractions recovered bydistillation can comprise mercaptans and sulfides as follows. In someaspects, the intermediate fraction can comprise C₁₀ to C₁₉ mercaptans,and the heavy fraction can comprise C₂₀ to C₃₀ mercaptans and C₂₀ to C₆₀sulfides. In other aspects, intermediate fraction can comprise C₁₀ toC₃₀ mercaptans and C₂₀ to C₃₀ sulfides, and the heavy fraction cancomprise C₃₁ to C₆₀ sulfides. In yet other aspects, a first intermediatefraction can comprise C₁₀ to C₁₉ mercaptans, a second intermediatefraction can comprise C₂₀ to C₃₀ mercaptans and C₂₀ to C₃₀ sulfides, andthe heavy fraction can comprise C₃₁ to C₆₀ sulfides. Intermediate andheavy fractions comprising both mercaptans and sulfides could be used asrecovered (e.g., mixed mercaptans/sulfides compositions), or can befurther processed to separate and recover further mercaptan compositionsand sulfide compositions.

In an aspect, an intermediate fraction can comprise at least about 25wt. %, alternatively at least about 30 wt. %, alternatively at leastabout 40 wt. %, alternatively at least about 50 wt. %, alternatively atleast about 75 wt. %, or alternatively at least about 85 wt. % branchedC₁₀₊ mercaptans. In such aspect, the branched C₁₀₊ mercaptans can beselected from the group consisting of a branched C₁₀ to C₃₀ mercaptanrepresented by Structure A-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure B-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In an aspect, the heavy fraction can comprise at least about 5, 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. % branchedC₂₀₊ sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ andR¹¹ can each independently be a branched C₁₀ to C₃₀ alkyl group derivedfrom a branched C₁₀ to C₃₀ monoolefin, and wherein the branched C₁₀ toC₃₀ alkyl group is selected from the group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀₊ sulfide; and wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively aC₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkyl group,alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkylgroup, or alternatively a C₉ to C₁₇ alkyl group.

In an aspect, a C₁₀₊ mercaptans composition can comprise C₁₀₊mercaptans, wherein at least a portion of the C₁₀₊ mercaptans comprisebranched C₁₀ to C₃₀ mercaptans. In an aspect, the branched C₁₀ to C₃₀mercaptans can comprise a branched C₁₀ to C₃₀ mercaptan represented byStructure A-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureB-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure C-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure D-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, or combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group. For purposes of the disclosure herein, branched C₁₀₊mercaptans refer to mercaptans (or thiols) that are characterized by thegeneral formula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group (asopposed to a linear alkyl group), i.e., an alkyl group substituted withalkyl substituents; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.Further, for purposes of the disclosure herein, a composition comprisingmercaptans, wherein at least a portion of the mercaptans are branchedC₁₀₊ mercaptans (e.g., branched C₁₀ to C₃₀ mercaptans as disclosedherein), can also be referred to as a “branched C₁₀₊ mercaptanscomposition.” In an aspect, the C₁₀₊ mercaptans composition can compriseany suitable amount of branched C₁₀ to C₃₀ mercaptans.

In an aspect, the C₁₀₊ mercaptans can further comprise non-branched C₁₀₊mercaptans, such as for example a linear C₁₀ to C₃₀ mercaptanrepresented by Structure M-1, a linear C₁₀ to C₃₀ mercaptan representedby Structure N-1, a linear C₁₀ to C₃₀ mercaptan represented by StructureO-1, a linear C₁₀ to C₃₀ mercaptan represented by Structure P-1, orcombinations thereof; wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In aspects where R⁹ is a methyl group, the C₁₀₊ mercaptans can furthercomprise non-branched C₁₀ mercaptans, as previously disclosed herein.The non-branched C₁₀ mercaptans can comprise 1-mercapto-decane(represented by Structure M), 4-mercapto-decane (represented byStructure N), 5-mercapto-decane (represented by Structure O),2-mercapto-decane (represented by Structure P), or combinations thereof.

In some aspects, a C₁₀₊ mercaptans composition can comprise at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % C₁₀₊ mercaptans, basedon the total weight of the C₁₀₊ mercaptans composition; wherein at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 75 wt. %,alternatively at least about 80 wt. %, or alternatively at least 85 wt.% of the C₁₀₊ mercaptans can be branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH, wherein R¹⁴ is a branchedalkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.In such aspects, the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH can be selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In other aspects, a C₁₀₊ mercaptans composition can comprise at leastabout 1 wt. %, alternatively at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % mercaptans, wherein at least a portion of the mercaptans can bebranched C₁₀ to C₃₀ mercaptans characterized by the general formulaR¹⁴—SH, wherein R¹⁴ is a branched alkyl group; and wherein R¹⁴ has from10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms,alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30carbon atoms, alternatively from 16 to 28 carbon atoms, or alternativelyfrom 18 to 26 carbon atoms. In such aspects, the branched C₁₀ to C₃₀mercaptans characterized by the general formula R¹⁴—SH can be selectedfrom the group consisting of a branched C₁₀ to C₃₀ mercaptan representedby Structure A-1, a branched C₁₀ to C₃₀ mercaptan represented byStructure B-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureC-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure D-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure E-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀mercaptan represented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In yet other aspects, a C₁₀₊ mercaptans composition can comprise atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % mercaptans;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at least85 wt. % of the mercaptans can be branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH, wherein R¹⁴ is a branchedalkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.In such aspects, the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH can be selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can compriseat least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. %mercaptans; wherein at least about 25, 30, 35, 40, 45, 50, 55, 60, 65,70, 75, 80, 85, 90, 95, or 99 wt. % of the mercaptans can be branchedC₁₀ to C₃₀ mercaptans characterized by the general formula R¹⁴—SH,wherein R¹⁴ is a branched alkyl group; and wherein R¹⁴ has from 10 to 30carbon atoms, alternatively from 11 to 30 carbon atoms, alternativelyfrom 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspects, the branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH can be selected from thegroup consisting of a branched C₁₀ to C₃₀ mercaptan represented byStructure A-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureB-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure C-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure D-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can comprisefrom at least about 50 wt. % to at least about 90 wt. %, alternativelyfrom at least about 55 wt. % to at least about 85 wt. %, oralternatively from at least about 60 wt. % to at least about 80 wt. %mercaptans, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the mercaptans can be branchedC₁₀ to C₃₀ mercaptans characterized by the general formula R¹⁴—SH,wherein R¹⁴ is a branched alkyl group; and wherein R¹⁴ has from 10 to 30carbon atoms, alternatively from 11 to 30 carbon atoms, alternativelyfrom 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspects, the branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH can be selected from thegroup consisting of a branched C₁₀ to C₃₀ mercaptan represented byStructure A-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureB-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure C-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure D-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can consist ofor consist essentially of branched C₁₀ to C₃₀ mercaptans characterizedby the general formula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group;and wherein R¹⁴ has from 10 to 30 carbon atoms, alternatively from 11 to30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternativelyfrom 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, oralternatively from 18 to 26 carbon atoms. In such aspects, the branchedC₁₀ to C₃₀ mercaptans characterized by the general formula R¹⁴—SH can beselected from the group consisting of a branched C₁₀ to C₃₀ mercaptanrepresented by Structure A-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure B-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can compriseat least about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH, wherein R¹⁴ is a branchedalkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.In such aspects, the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH can be selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can comprisemercaptans, wherein at least about 50, 55, 60, 65, 70, 75, 80, 85, 90,95, or 99 wt. % of the mercaptans are branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH, wherein R¹⁴ is a branchedalkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.In such aspects, the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH can be selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In an aspect, a C₂₀₊ sulfides composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀₊ sulfides, and whereinat least a portion of the C₂₀₊ sulfides comprise branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹can each independently be an alkyl group, and wherein at least a portionof the alkyl groups comprises a branched C₁₀ to C₃₀ alkyl group,alternatively a branched C₁₁ to C₃₀ alkyl group, alternatively abranched C₁₂ to C₃₀ alkyl group, alternatively a branched C₁₄ to C₃₀alkyl group, alternatively a branched C₁₆ to C₂₈ alkyl group, oralternatively a branched C₁₈ to C₂₆ alkyl group. In such aspect, thealkyl group (e.g., a branched C₁₀ to C₃₀ alkyl group as R¹⁰, R¹¹) cancomprise a functional group derived from an olefin, wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin represented by Structure I-1,a branched C₁₀ to C₃₀ monoolefin represented by Structure J-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure K-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure L-1, or combinationsthereof; wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ toC₂₁ alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively aC₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group. As previously disclosed herein,for purposes of the disclosure herein a sulfide (e.g., a branched C₂₀ toC₆₀ sulfide) will be referred to by the total number of carbon atoms (asopposed to the number of carbons of only one of the alkyl groups presentin a dialkyl sulfide). For example, a H₂₁C₁₀—S—C₁₀H₂₁ sulfide will bereferred to as a C₂₀ sulfide (rather than a C₁₀ sulfide); aH₂₅C₁₂—S—C₁₄H₂₉ sulfide will be referred to as a C₂₆ sulfide (ratherthan a C₁₂ sulfide or a C₁₄ sulfide); a H₄₅C₂₂—S—C₂₂H₄₅ sulfide will bereferred to as a C₄₄ sulfide (rather than a C₂₂ sulfide); etc. Forpurposes of the disclosure herein, branched C₂₀ to C₆₀ sulfides refer tosulfides (or thioethers) that are characterized by the general formulaR¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ are each independently a branchedC₁₀ to C₃₀ alkyl group, alternatively a branched C₁₁ to C₃₀ alkyl group,alternatively a branched C₁₂ to C₃₀ alkyl group, alternatively abranched C₁₄ to C₃₀ alkyl group, alternatively a branched C₁₆ to C₂₈alkyl group, or alternatively a branched C₁₈ to C₂₆ alkyl group (asopposed to a linear alkyl group), i.e., an alkyl group substituted withalkyl substituents. Stated alternatively, branched C₂₀ to C₆₀ sulfidesrefer to sulfides wherein both R¹⁰ and R¹¹ are branched C₁₀ to C₃₀ alkylgroups, wherein R¹⁰ and R¹¹ can be the same or different. Further, forpurposes of the disclosure herein, a composition comprising sulfides,wherein at least a portion of the sulfides are branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹, wherein both R¹⁰ and R¹¹ areeach independently an alkyl group, wherein the alkyl group comprises abranched C₁₀ to C₃₀ alkyl group (e.g., a functional group derived froman olefin, and wherein the olefin comprises a branched C₁₀ to C₃₀monoolefin as disclosed herein), can also be referred to as a “branchedC₂₀₊ sulfides composition.” In an aspect, the C₂₀₊ sulfides compositioncan comprise any suitable amount of branched C₂₀ to C₆₀ sulfides.

In an aspect, a C₂₀₊ sulfides composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀₊ sulfides, and whereinat least a portion of the C₂₀₊ sulfides comprise branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹ caneach independently be a branched C₁₀ to C₃₀ alkyl group derived from abranched C₁₀ to C₃₀ monoolefin, and wherein the branched C₁₀ to C₃₀alkyl group is selected from the group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ to C₆₀ sulfide; and wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group. In an aspect, thebranched Co to C₃₀ monoolefin can comprise a branched C₁₀ to C₃₀monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In an aspect, the C₂₀ to C₆₀ sulfides can further comprise non-branchedC₂₀ to C₆₀ sulfides and/or partially branched C₂₀ to C₆₀ sulfidesrepresented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ (in thecase of non-branched C₂₀ to C₆₀ sulfides) or one of the R¹⁰ and R¹¹ (inthe case of partially-branched C₂₀ to C₆₀ sulfides) can be a linear C₁₀to C₃₀ alkyl group derived from a linear C₁₀ to C₃₀ monoolefin, such asfor example a linear C₁₀ to C₃₀ monoolefin represented by Structure Q-1,a linear C₁₀ to C₃₀ monoolefin represented by Structure R-1, a linearC₁₀ to C₃₀ monoolefin represented by Structure S-1, or combinationsthereof; wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ toC₂₁ alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively aC₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group.

For purposes of the disclosure herein, the non-branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹ are the sulfides whereinboth R¹⁰ and R¹¹ are each independently a linear C₁₀ to C₃₀ alkyl groupderived from a linear C₁₀ to C₃₀ monoolefin. Further, for purposes ofthe disclosure herein, the partially branched C₂₀ to C₆₀ sulfidesrepresented by structure R¹⁰—S—R¹ are the sulfides wherein one of theR¹⁰ and R¹¹ is a linear C₁₀ to C₃₀ alkyl group derived from a linear C₁₀to C₃₀ monoolefin, while the other one of the R¹⁰ and R¹¹ is a branchedC₁₀ to C₃₀ alkyl group derived from a branched C₁₀ to C₃₀ monoolefin asdescribed herein.

In aspects where R⁹ is a methyl group, the linear C₁₀ to C₃₀ monoolefincan further comprise linear C₁₀ monoolefins, as previously disclosedherein. The linear C₁₀ monoolefins can comprise 4-decene (represented byStructure Q), 5-decene (represented by Structure R), 1-decene(represented by Structure S), or combinations thereof.

In some aspects, a C₂₀₊ sulfide composition can comprise sulfides,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of the sulfidescan be branched C₂₀ to C₆₀ sulfides represented by structure R¹⁰—S—R¹¹,wherein both R¹⁰ and R¹¹ can each independently be a functional groupderived from an olefin, and wherein the olefin comprises a branched C₁₀to C₃₀ monoolefin, alternatively a branched C₁₁ to C₃₀ monoolefin,alternatively a branched C₁₂ to C₃₀ monoolefin, alternatively a branchedC₁₄ to C₃₀ monoolefin, alternatively a branched C₁₆ to C₂₈ monoolefin,or alternatively a branched C₁₈ to C₂₆ monoolefin. In such aspects, theolefin can comprise a branched C₁₀ to C₃₀ monoolefin represented byStructure I-1, a branched C₁₀ to C₃₀ monoolefin represented by StructureJ-1, a branched C₁₀ to C₃₀ monoolefin represented by Structure K-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure L-1, orcombinations thereof.

In other aspects, a C₂₀₊ sulfide composition can comprise at least about1 wt. %, alternatively at least about 5 wt. %, alternatively at leastabout 10 wt. %, alternatively at least about 20 wt. %, alternatively atleast about 30 wt. %, alternatively at least about 40 wt. %,alternatively at least about 50 wt. %, alternatively at least about 60wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. % sulfides,wherein at least a portion of the sulfides can be branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹can each independently be a functional group derived from an olefin, andwherein the olefin comprises a branched C₁₀ to C₃₀ monoolefin,alternatively a branched C₁₁ to C₃₀ monoolefin, alternatively a branchedC₁₂ to C₃₀ monoolefin, alternatively a branched C₁₄ to C₃₀ monoolefin,alternatively a branched C₁₆ to C₂₈ monoolefin, or alternatively abranched C₁₈ to C₂₆ monoolefin. In such aspects, the olefin can comprisea branched C₁₀ to C₃₀ monoolefin represented by Structure I-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure J-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure K-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure L-1, or combinations thereof.

In other aspects, a C₂₀₊ sulfide composition can comprise at least about1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85,90, 95, or 99 wt. %, sulfides, wherein at least about 1, 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. %of the sulfides can be branched C₂₀ to C₆₀ sulfides represented bystructure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently bea functional group derived from an olefin, and wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin, alternatively a branched C₁₁to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀ monoolefin,alternatively a branched C₁₄ to C₃₀ monoolefin, alternatively a branchedC₁₆ to C₂₈ monoolefin, or alternatively a branched C₁₈ to C₂₆monoolefin. In such aspects, the olefin can comprise a branched C₁₀ toC₃₀ monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In yet other aspects, a C₂₀₊ sulfide composition can comprise at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, or alternatively at least about 25 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ to C₆₀ sulfidesrepresented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can eachindependently be a functional group derived from an olefin, and whereinthe olefin comprises a branched C₁₀ to C₃₀ monoolefin, alternatively abranched C₁₁ to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀monoolefin, alternatively a branched C₁₄ to C₃₀ monoolefin,alternatively a branched C₁₆ to C₂₈ monoolefin, or alternatively abranched C₁₈ to C₂₆ monoolefin. In such aspects, the olefin can comprisea branched C₁₀ to C₃₀ monoolefin represented by Structure I-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure J-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure K-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure L-1, or combinations thereof.

In still yet other aspects, a C₂₀₊ sulfide composition can comprise fromat least about 10 wt. % to at least about 30 wt. %, alternatively fromat least about 12.5 wt. % to at least about 22.5 wt. %, or alternativelyfrom at least about 15 wt. % to at least about 20 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ to C₆₀ sulfidesrepresented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can eachindependently be a functional group derived from an olefin, and whereinthe olefin comprises a branched C₁₀ to C₃₀ monoolefin, alternatively abranched C₁₁ to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀monoolefin, alternatively a branched C₁₄ to C₃₀ monoolefin,alternatively a branched C₁₆ to C₂₈ monoolefin, or alternatively abranched C₁₈ to C₂₆ monoolefin. In such aspects, the olefin can comprisea branched C₁₀ to C₃₀ monoolefin represented by Structure I-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure J-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure K-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure L-1, or combinations thereof.

In still yet other aspects, a C₂₀₊ sulfide composition can consist of orconsist essentially of branched C₂₀ to C₆₀ sulfides represented bystructure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently bea functional group derived from an olefin, and wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin, alternatively a branched C₁₁to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀ monoolefin,alternatively a branched C₁₄ to C₃₀ monoolefin, alternatively a branchedC₁₆ to C₂₈ monoolefin, or alternatively a branched C₁₈ to C₂₆monoolefin. In such aspects, the olefin can comprise a branched C₁₀ toC₃₀ monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In still yet other aspects, a C₂₀₊ sulfide composition can comprise atleast about 5 wt. %, alternatively at least about 10 wt. %,alternatively at least about 15 wt. %, or alternatively at least about20 wt. % branched C₂₀ to C₆₀ sulfides represented by structureR¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently be afunctional group derived from an olefin, and wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin, alternatively a branched C₁₁to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀ monoolefin,alternatively a branched C₁₄ to C₃₀ monoolefin, alternatively a branchedC₁₆ to C₂₈ monoolefin, or alternatively a branched C₁₈ to C₂₆monoolefin. In such aspects, the olefin can comprise a branched C₁₀ toC₃₀ monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In still yet other aspects, a C₂₀₊ sulfide composition comprises atleast about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % branched C₂₀ to C₆₀ sulfides representedby structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independentlybe a functional group derived from an olefin, and wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin, alternatively a branched C₁₁to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀ monoolefin,alternatively a branched C₁₄ to C₃₀ monoolefin, alternatively a branchedC₁₆ to C₂₈ monoolefin, or alternatively a branched C₁₈ to C₂₆monoolefin. In such aspects, the olefin can comprise a branched C₁₀ toC₃₀ monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In an aspect, a C₁₀₊ mercaptans/C₂₀₊ sulfides composition can compriseone or more mercaptans and one or more sulfides of the type disclosedherein. For purposes of the disclosure herein, a composition comprising(i) mercaptans, wherein at least a portion of the mercaptans arebranched C₁₀ to C₃₀ mercaptans, and (ii) sulfides, wherein at least aportion of the sulfides are branched C₂₀ to C₆₀ sulfides, can also bereferred to as a “branched C₁₀₊ mercaptans/branched C₂₀₊ sulfidescomposition.” In an aspect, the C₁₀₊ mercaptans/C₂₀₊ sulfidescomposition can comprise any suitable amount of branched C₁₀ to C₃₀mercaptans, and any suitable amount of branched C₂₀ to C₆₀ sulfides.

In an aspect, a C₁₀₊ mercaptans/C₂₀₊ sulfides composition can comprise(A) at least about 1 wt. %, alternatively at least about 5 wt. %,alternatively at least about 10 wt. %, alternatively at least about 15wt. %, alternatively at least about 20 wt. %, alternatively at leastabout 25 wt. %, alternatively at least about 30 wt. %, alternatively atleast about 40 wt. %, alternatively at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 80 wt. %, alternatively at leastabout 90 wt. %, alternatively at least about 95 wt. %, or alternativelyat least about 99 wt. % mercaptans, wherein at least a portion of themercaptans can be branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group; andwherein R¹⁴ has from 10 to 30 carbon atoms, alternatively from 11 to 30carbon atoms, alternatively from 12 to 30 carbon atoms, alternativelyfrom 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, oralternatively from 18 to 26 carbon atoms; and (B) at least about 1 wt.%, alternatively at least about 5 wt. %, alternatively at least about 10wt. %, alternatively at least about 20 wt. %, alternatively at leastabout 30 wt. %, alternatively at least about 40 wt. %, alternatively atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % sulfides,wherein at least a portion of the sulfides can be branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹can each independently be a functional group derived from an olefin, andwherein the olefin comprises a branched C₁₀ to C₃₀ monoolefin,alternatively a branched C₁₁ to C₃₀ monoolefin, alternatively a branchedC₁₂ to C₃₀ monoolefin, alternatively a branched C₁₄ to C₃₀ monoolefin,alternatively a branched C₁₆ to C₂₈ monoolefin, or alternatively abranched C₁₈ to C₂₆ monoolefin. In such aspect, the branched C₁₀ to C₃₀mercaptans characterized by the general formula R¹⁴—SH can be selectedfrom the group consisting of a branched C₁₀ to C₃₀ mercaptan representedby Structure A-1, a branched C₁₀ to C₃₀ mercaptan represented byStructure B-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureC-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure D-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure E-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀mercaptan represented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and the olefincan comprise a branched C₁₀ to C₃₀ monoolefin represented by StructureI-1, a branched C₁₀ to C₃₀ monoolefin represented by Structure J-I, abranched C₁₀ to C₃₀ monoolefin represented by Structure K-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure L-1, or combinationsthereof.

In an aspect, a C₁₀₊ mercaptan/C₂₀₊ sulfide composition can comprise C₁₀to C₃₀ mercaptans characterized by the general formula R¹⁴—SH and/or C₂₀to C₆₀ sulfides represented by structure R¹⁰—S—R¹¹ that are formed byreacting an olefin feedstock comprising olefins with H₂S as described inmore detail herein, wherein the olefins present in the olefin feedstockprovide the alkyl group represented by R¹⁰, R¹¹, and R¹⁴. In suchaspects, the R¹⁰ and R¹¹ groups of the C₂₀ to C₆₀ sulfides and/or theR¹⁴ group of the C₁₀ to C₃₀ mercaptans are provided by or derived fromthe counterpart R¹⁰, R¹¹, and R¹⁴ groups present in the olefins in theolefin feedstock. In an aspect, R¹⁰, R¹¹, and R¹⁴ can each independentlybe an alkyl group, wherein at least a portion of the alkyl groups cancomprise a functional group derived from an olefin, wherein the olefinis present in a feedstock as disclosed herein (e.g., a first C₁₀ to C₃₀feedstock; a second C₁₀ to C₃₀ feedstock).

In an aspect, a C₁₀₊ mercaptans composition and/or a C₁₀₊mercaptans/C₂₀₊ sulfides composition comprising equal to or greater thanabout 25 wt. % C₁₀₊ branched mercaptans as disclosed herein canadvantageously have an odor less unpleasant and less offensive than anodor of an otherwise similar composition comprising equal to or greaterthan about 25 wt. % n-decyl mercaptan, as perceived by equal to orgreater than about 51% of human subjects exposed to the odor of eachcomposition.

In an aspect, a C₁₀₊ mercaptans composition and/or a C₁₀₊mercaptans/C₂₀₊ sulfides composition comprising equal to or greater thanabout 25 wt. % C₁₀₊ branched mercaptans as disclosed herein canadvantageously have an odor less unpleasant than an odor of an otherwisesimilar composition comprising equal to or greater than about 25 wt. %n-dodecyl mercaptan and/or tert-dodecyl mercaptan, as perceived by equalto or greater than about 51% of human subjects exposed to the odor ofeach composition. Additional advantages of the C₁₀₊ mercaptanscompositions, C₂₀₊ sulfides compositions, and C₁₀₊ mercaptans/C₂₀₊sulfides compositions and processes of producing same as disclosedherein can be apparent to one of skill in the art viewing thisdisclosure.

EXAMPLES

The subject matter having been generally described, the followingexamples are given as particular embodiments of the disclosure and todemonstrate the practice and advantages thereof. It is understood thatthe examples are given by way of illustration and are not intended tolimit the specification of the claims to follow in any manner.

Hydrogen sulfide (H₂S) and a feedstock comprising branched C₁₀monoolefins were reacted in the presence of various initiating agents:UV radiation, an acid catalyst, and a hydrodesulfurization (HDS)catalyst.

Various feedstocks (e.g., olefin feedstocks) were used for reacting withH₂S to produce mercaptans and/or sulfides. More specifically, olefinfeedstocks obtained from 1-hexene production processes were used asfeedstocks for reacting with H₂S to produce mercaptans. Gaschromatography (GC)-mass spectrometry (MS) (GC-MS) and nuclear magneticresonance (NMR) spectroscopy were used for analyzing the composition ofolefin feedstocks obtained from 1-hexene production processes.

The compositions comprising C₁₀ monoolefins, i.e., the feedstocksobtained from a 1-hexene production process, were analyzed by gaschromatography-mass spectrometry (GC-MS) using a 15 m×0.25 mm×0.5 μmDB-5 column and/or a 40 m×0.1 mm×0.1 μm DB-1 column to determinecomponent identities, and standard gas chromatography (GC) using a 60m×0.32 mm×1 μm DB-1 column to determine the quantity of the componentspresent in the compositions. As described previously, these compositionsare measured in area %, which is substantially similar and analogous towt. %.

Table 1 provides representative information about the composition ofsuch an olefin feedstock obtained from 1-hexene production processes toreact with H₂S to produce mercaptans—Samples #1-4 in Example 1.

TABLE 1 Chemical GC Area % Normalized % cyclohexane 2.148 octene 0.036C₈ olefins 1.17 1.24 1-octene 1.135 octane 0.146 octane 0.15 0.16ethylbenzene 1.684 3-propyl-1-heptene 14.590 C₁₀ olefins 84.16 89.11decene 0.164 4-ethyl-1-octene 13.134 5-methyl-1-nonene 32.144 decene0.647 2-butyl-1-hexene 9.960 decene 0.320 4/5 decene 9.116 1-decene4.086 decane 0.360 decane 0.36 0.38 2-ethyl-1-hexanol 1.379 dodeceneisomers 0.448 C₁₂ olefins 1.29 1.37 1-dodecene 0.842 dodecane 0.182dodecane 0.18 0.19 tetradecenes 6.710 C₁₄ olefins 6.71 7.11 tetradecane0.198 tetradecane 0.2 0.21 octadecene 0.222 C₁₈ olefins 0.22 0.232-ethylhexyl-2- 0.069 ethylhexanoate Unknowns 0.281 Total 100.000 totalolefins 94.44 99.06 Normalized to include only octane, decane, dodecane,tetradecane, and C₈, C₁₀, C₁₂, C₁₄, and C₁₈ olefins

As mentioned previously, the olefin feedstock was produced from thetrimerization of ethylene in a 1-hexene production process. As shown inTable 1, the total product content of this particular olefin feedstocksample (excluding the compounds that are not products of the 1-hexeneprocess) is 94.44 area %, and 84.16 area % of the feedstock is C₁₀olefin isomers. The C₁₀ olefins represent over 89 area % of the totalolefin content when the sample is normalized to remove the compoundsthat are not products of the 1-hexene process. Cyclohexane,ethylbenzene, and 2-ethylhexanol can be present in the olefin feedstockas residual components of the 1-hexene oligomerization process. Thestructures of C₁₀ isomers that can be present in the olefin feedstockare shown in Table 2.

TABLE 2 Decene Fraction Olefin Major UV Product Major Acid CatalystProduct 5-methyl-1- nonene 32.14% (38.19)

3-propyl-1- heptene 14.59% (17.33)

4-ethyl- 1-octene 13.13% (15.60)

2-butyl-1- hexene 9.96% (11.83)

4/5 decene 9.12% (10.83)

1-decene 4.09% (4.86)

In Table 2, the first column provides the name of the isomer, the GCarea % of that component in the feedstock from Table 1, and thenormalized amount of the isomer typically found in the C₁₀ fraction ofthe feedstock. Table 2 also displays the structure of the mercaptansthat are produced from the C₁₀ olefin isomers. The second column showsthe structure of the major C₁₀ olefin isomers in the feedstock; thethird column displays the structure of the major mercaptan isomersproduced by a UV-initiated reaction with H₂S; and the fourth columndisplays the structure of the major mercaptan isomers produced by acidcatalysis, such as Filtrol® 24 or Filtrol® 24X.

A sample of the olefin feedstock was fractionated (e.g., distilled) andonly the C₁₀ fraction was isolated in high purity (e.g., a purifiedfeedstock). This product was submitted for H¹ and C¹³ NMR. The NMRanalysis (in mol %) was consistent the GC-MS results. The NMR confirmedthat about 11 mol % of the total purified feedstock was vinylidene (2butyl-1-hexene isomer) and about 11 mol % of the total purifiedfeedstock was internal olefins (linear decene isomers). The nomenclaturefor the various C₁₀ isomer products is shown in Table 3.

TABLE 3 Acid-catalyzed C₁₀ Olefin UV-initiated Mercaptans Mercaptans5-methyl-1-nonene 5-methyl-1-mercapto-nonane 5-methyl-2- mercapto-nonane3-propyl-1-heptene 3-propyl-1-mercapto-heptane 3-propyl-2-mercapto-heptane 4-ethyl-1-octene 4-ethyl-1-mercapto-octane4-ethyl-mercapto- octane 2-butyl-1-hexene 2-butyl-1-mercapto-hexane5-mercapto-5- methyl-nonane 4-decene 4-mercapto-decane 4-mercapto-decane5-mercapto-decane 5-mercapto-decane 5-decene 4-mercapto-decane4-mercapto-decane 5-mercapto-decane 5-mercapto-decane 1-decene1-mercapto-decane 2-mercapto-decane

Reaction of H₂S with the olefin feedstock (e.g., a feedstock comprisingbranched C₁₀ monoolefins) by UV-initiation (e.g., using UV radiation)yielded mostly primary mercaptans, since the terminal olefin andvinylidene isomers yield predominately the anti-Markovnikov product. Theminor components were secondary mercaptans from the terminal olefin anda tertiary mercaptan from the vinylidene isomer. Typically,UV-initiation of a terminal olefin produced primary mercaptans in 92-96area % range and secondary mercaptans in 4-8 area % range. The linearinternal olefin isomers present in the feedstock primarily producedsecondary mercaptan isomers. Thus, for the composition of the feedstockdisclosed herein, the distribution of mercaptans (i.e., the distributionwithin the C₁₀ fraction) in the resulting reaction product waspredominately primary mercaptans at about 80-90 area %. Secondarymercaptans were present at 10-20 area %, and tertiary mercaptans werepresent at about 0-3 area %. These ranges were calculated by NMRanalysis of the reaction product.

Reaction of H₂S with a feedstock comprising branched C₁₀ monoolefinsover an acid catalyst (such as Filtrol® 24 or Filtrol® 24X) produced asthe major product the Markovnikov product. Thus, the major mercaptanisomers comprised secondary mercaptans with some tertiary mercaptans.The relative ratio of mercaptans was estimated at 85-90 area % secondarymercaptans and 10-15 area % tertiary mercaptans.

Reaction of H₂S with a feedstock comprising branched C₁₀ monoolefins inthe presence of a hydrodesulfurization (HDS) catalyst (such as HaldorTopsoe TK-554 or TK0570) produced mercaptans generally similar indistribution to those produced by acid catalysis, which is theMarkovnikov distribution. However, the HDS catalyst also produced asignificant amount of the anti-Markovnikov product depending on theconditions used in the reaction step. Thus, under the conditions used inthis disclosure, the product produced by the HDS catalyst was a blend ofthe product produced via acid catalysis with some of the componentsproduced by the UV-initiated reaction.

As will be appreciated by one of skill in the art, and with the help ofthis disclosure, the actual composition of the resultant crude productwill ultimately depend on a number of factors including composition ofthe feedstock; the ratio of H₂S to olefin that is used to produce thethiols; the catalytic method and reaction conditions used to react theH₂S and olefin (UV-initiated, acid catalysis, or HDS catalysis) toproduce the crude product; etc. The final product (e.g., any cutsseparated from the crude to form, for example, a commercial product)will also depend on the purification step to remove lights and whether afinal product containing both mercaptan and sulfide fractions is desiredor just one of the fractions, e.g., a mercaptan fraction or a sulfidefraction, is desired.

H₂S to Olefin Molar Ratio:

The H₂S to olefin molar ratio can be an important parameter indetermining the amount of mercaptan and sulfide produced during thereaction step. This can be true regardless of the catalytic methodemployed. Without wishing to be limited by theory and in general, thehigher the H₂S to olefin molar ratio, the greater the amount ofmercaptans that will be produced compared to the amount of sulfidesproduced.

A general reaction scheme for addition of H₂S to an olefin is shown inFIG. 1, regardless of catalytic method. For a C₁₀ olefin fraction, R, R′and R″ can be H or C₁-C₈ with the total of R+R′+R″=8 carbon atoms. For1-decene, R═H and R′═H and R″=8 and can be a linear or branched alkylgroup. For the major isomers in a C₁₀ olefin fraction (e.g., a secondfeedstock as disclosed herein), 5-methyl-1-nonene: R═H and R′═H andR″=8, but the alkyl group contains branching at the third carbon atom ofthe C₈ fraction.

A sulfide fraction can be produced by further reaction of a mercaptanisomer with an olefin. The generic structures of such sulfides are shownin FIG. 1 and this fraction can consist of a variety of isomers withseveral possible combinations of sulfide structures depending on whetherthe sulfide is primary to primary, primary to secondary, primary totertiary, secondary to secondary, secondary to tertiary, or tertiary totertiary. The structures are complicated by the fact that on the twoportions of the sulfide the R, R′ and R″ value can be the same ordifferent depending on which mercaptan isomer reacts with which olefinisomer. The total number of carbon atoms of the two portions of thesulfide can also have different values for R+R′+R″, although the mostdominant combination will be where both sides each have a total sum of 8carbon atoms since the C₁₀ fraction predominates in the first feedstockand in the second feedstock.

Reaction Conditions:

Three different reaction methods were used to perform the reaction ofH₂S with a feedstock comprising branched C₁₀ monoolefins: UV-initiation,acid catalysis, and HDS catalysis.

H₂S Removal:

In laboratory experimentation, H₂S was removed using a rotovaporapparatus under conditions of reduced pressure. Under these conditions,H₂S was removed without removing significant quantities of lightcompounds.

Analytical Methods:

The weight percentage of thiol sulfur (wt. % SH) was determinedanalytically by titration using iodine in water as the titrant andmethylene chloride/isopropanol as the solvent system. Such titration canalso be done by using a silver nitrate titration method. Total sulfurwas measured by X-ray using a model SLFA-20 Horiba sulfur-in-oilanalyzer. GC analysis of the reaction product was performed using anAgilent Technologies 7890A GC. A 2m×0.25 mm×1.0 m film DB-1 capillarycolumn was used for the separation. Operating conditions were asfollows: 70° C. initial temperature, 2 min hold time, 8° C./min ramprate to 200° C. and then 15° C./min ramp rate to 300° C. and hold for 10minutes. A 2 ml/min helium flow rate at constant flow conditions wasused. A flame ionization detector was used. The injector temperature wasset at 275° C. and the detector temperature at 300° C. As describedpreviously, these data from these compositions were reported in area %,which is substantially similar and analogous to wt. %. Olefin conversionwas monitored using Raman spectroscopy with a Kaiser Optical System RXN24-channel spectrometer. The peak centered at 1640 cm⁻¹ was the vinylolefin, while the peak centered at about 1670 cm⁻¹ was the internalolefin.

Example 1

UV-initiation reactions were performed using either a 1.5 L or a 5-literUV reactor equipped with a 100 watt lamp and ballast. The two reactorsare substantially the same configuration, and the only difference inoperation is the amount of reactants added to the reactor. To 800 g ofmixed C₁₀ olefin (or 2.7 kg, if using the larger reactor), 5 g (or 16.7g) of triethyl phosphite was added and 0.2 kg (or 0.67 kg) H₂S wascharged after sealing the reactor. The reaction mixture was stirred at500-1,000 RPM. The reaction temperature was controlled with a bath setat 25° C., but the heat of reaction did reach about 40° C. The lampoperated at 1.1-1.5 amps and 28-103 volts over the course of thereaction, operating at lower amps and higher voltage as it warmed up.The reaction pressure was 220-280 psig (1,516 kPag-1,930 kPag) duringthe actual reaction time. The reaction was completed in about 30 minutesbased on the results of Raman spectroscopy but was allowed to continuefor 60 minutes to ensure completion. Table 4 shows the results of fourreactions by UV-initiation, wherein the reactions produced Samples #1,#2, #3, and #4.

TABLE 4 Sample # 1 1a 2 2a 3 3a 4 4a Olefin 800 930 930 930 Feedstockwt. H₂S wt. 200 2300 2300 2300 H2S:Olefin 1.0 10.2 10.2 10.2 Molar RatioPhosphite TEP TEP TEP TBP Phosphite wt. 5.0 1.0 1.0 1.0 wt. % 0.63 0.110.11 0.11 Phosphite Reaction Time 70.0 40.0 45.0 45.0 (minutes) % Raman97.0 98.0 97.3 97.2 Conversion wt. % SH 11.2 15.8 16.6 16.8 16.4 wt. %Total S 15.4 16.3 17.5 17.9 16.9 GC Analysis area % Lights 8.78 0.0317.07 3.61 6.96 Light 1.10 0.22 1.01 0.015 3.75 3.45 Intermediate C₁₀ SHRegion 51.85 56.84 76.04 82.45 82.38 84.14 78.29 84.02 Intermediate 4.965.71 7.91 9.04 4.23 5.75 4.26 5.82 Heavies Sulfides 33.31 37.20 7.988.50 6.03 10.10 7.05 10.15 TEP = triethyl phosphite; TBP = tributylphosphite.

Samples #1-4 were prepared using samples of an olefin feedstockcomposition comparable to that shown in Table 1. Samples #1a, #2a, #3a,and #4a were prepared by distilling the crude reaction product, Samples#1, #2, #3, and #4, respectively. The distillation process proceeded asfollows: The first 7 fractions removed from the crude reaction productwere considered to be the light fractions. This distillation step wasconsidered to be complete when the kettle temperature increased from100° C. to 121° C. and the head temperature increased from roomtemperature to 98.9° C. Cuts 8-13 were considered to be the intermediatefractions and included the C₁₀ mercaptans. These cuts were collected ata kettle temperature of 122° C. to 154° C. and a head temperature of 99°C. to 105° C. Cuts 14 and 15 were collected at kettle and headtemperatures of from 122° C. to 154° C. and 103.4° C. to 107.2° C.,respectively. These cuts and whatever remained in the kettle wereconsidered the heavies. The head temperature was allowed to increasefrom room temperature to 107.2° C. before the distillation was stopped.For a typical distillation, only the light fractions were distilled(e.g., removed) and the reaction product was what remained (e.g.,including C₁₀ mercaptans and C₂₀ sulfides) in the kettle after thelights were removed.

The relative amount of C₁₀ mercaptan isomers, intermediate mercaptans(e.g., non-C₁₀ mercaptans such as C₁₂ to C₁₆ mercaptans) and sulfideheavies (e.g., C₂₀ sulfides) depended on the ratio of H₂S to olefinduring the reaction step. Sample #1 was prepared at a 1:1 ratio of H₂Sper olefin to maximize the amount of sulfide content. Conventionalwisdom would suggest that the C₁₀ mercaptan fraction would have toostrong of an odor to be acceptable for certain applications, and thatthe sulfide fraction might have a better odor. Surprisingly andunexpectedly, after removing Sample #1 from the reactor and venting offthe residual H₂S using a rotovapor apparatus, the odor of this crudereaction product (Sample #1) was good.

FIG. 2 displays a GC trace of reactor crude Sample #1 (after removal ofresidual H₂S). FIG. 3 displays a GC trace of Sample #2 after removal oflights, designated as Sample 2a. Comparison of the GC traces in FIGS. 2and 3 indicates successful removal of the majority of the lights fromthe product stream, which include the cyclohexane, ethylbenzene,2-ethylhexanol and residual octane. Because the run (to obtain Sample#1) was performed at a low H₂S to olefin ratio, the amount of C₁₀mercaptan isomers (peaks at 3.8-6.5 minutes) accounted for 56.8 area %of the kettle product, as shown in FIG. 2. The intermediate cut (peaksat 6.5-14 minutes) included mercaptans produced from the C₁₂ to C₁₆olefins present in the olefin feedstock stream and accounted for 5.7area % of this particular sample. The heavies cut (peaks at >14 minuteretention time) included the sulfides, primarily C₁₀H₂₁—S—C₁₀H₂₁ isomersplus higher sulfides from combinations with other olefins in the mixedfeed. It is believed that any C₁₈ mercaptans that may have been producedeluted with the sulfide peaks. The amount of C₁₈ that could be presentwas estimated at about 0.2 area %. In Sample #1, the sulfide fractionaccounted for about 37.2 area % of the product composition. The amountof the intermediate fraction was primarily dependent on the amount ofC₁₄ olefin isomers that were present in the olefin feed stream. Analysisof several samples showed that this intermediate fraction ranged from4-10 area %.

FIG. 4 displays a GC trace of reactor crude Sample #3, after removal ofresidual H₂S. FIG. 5 displays a GC trace of kettle product Sample #3a,after removal of lights. FIGS. 4 and 5 compare GC results of productproduced at a 10:1 H₂S to olefin molar ratio. The observed trends aresimilar to the trends seen in FIGS. 2 and 3, and the primary differenceis in the ratio of C₁₀ mercaptan isomers to the sulfide fraction. Thisdifference is the result of increasing the ratio of H₂S to olefinfeedstock used in the reaction. The type and relative amounts of theisomers in the C₁₀ mercaptan fraction are essentially unchanged, and thecompositions of the sulfide heavies fractions are similar. What ischanged is the relative amount of the C₁₀ mercaptan fraction compared tothe sulfide heavies fraction, as in the sample with a lower H₂S:olefinsratio, there is significantly more of the sulfide fraction than themercaptan fraction. This result is not altogether unexpected, althoughfurther experimentation would allow one of skill in the art to optimizethe H₂S to olefins ratio to obtain a specific ratio of mercaptans tosulfides.

The main difference between Sample #3a and Sample #1a is the relativeamounts of C₁₀ mercaptan isomers, intermediate mercaptans, and sulfides.As expected, when the reaction was performed at a higher molar ratio ofH₂S per olefin, the resulting reaction product contained a greateramount of C₁₀ mercaptan isomers (84.1 area % vs. 56.8 area %) and muchless sulfide (10.1 area % vs. 37.2 area %). The removal of lights wasdone using a simple lab distillation unit, wherein the distillationcolumn was 12″ long and 1″ in diameter and was packed with a stainlesssteel sponge. Distillations were performed in batch mode at 9-10 torrvacuum pressure and an overhead temperature of about 100° C.-103° C. anda kettle temperature of about 125° C.-150° C. The lights were collectedoverhead while trying to minimize the amount of C₁₀ mercaptan isomersthat were lost with this overhead fraction.

The composition of the UV-produced product can be described in broadterms as follows: a feedstock was reacted with H₂S; removal of H₂S afterthe reaction yielded a crude reaction product. Subsequent removal of thelights fraction to yields a kettle product, which can be used “as is”(e.g., a composition comprising both mercaptans and sulfides) or can befurther separated into one or more products or cuts corresponding to adesired compound or combination of compounds (e.g., a C₁₀ mercaptanfraction, an intermediate mercaptan fraction, and/or a heavy/sulfidefraction). In broad terms, the product consists of three generalfractions as produced from the kettle product after removal of theunwanted lights fraction. The C₁₀ mercaptan fraction comprised from50-100 wt. % of the kettle product. The mercaptan functionality of theC₁₀ mercaptan fraction was 80-90% primary mercaptan, 5-18% secondarymercaptan and 0-3% tertiary mercaptan. This was the fraction that elutedin the 3.8-6.5 minute range under the GC conditions used. Theintermediate fraction, which eluted in the 6.5-14 minute region, waspredominately mercaptan isomers in the C₁₂ to C₁₈ range with adistribution of functionality that can be similar to that for the C₁₀isomer fraction. The intermediate fraction comprised from 0 to 12 area %of the kettle product. The heavy fraction (>14 minute retention time)consisted essentially of sulfides, primarily of formula C₁₀H₂₁—S—C₁₀H₂₁isomers, as well as sulfides from C₁₂, C₁₄, C₁₆ or C₁₈ olefins andmercaptans or the asymmetric sulfides produced from the variouscombinations. These sulfide components comprised from 0-70 area % of thekettle product, depending on the reaction conditions used.

Example 2

Acid Catalysis produced a different distribution of isomer products thanthose produced by UV-initiation reaction of H₂S and the olefin feedstockcomprising branched C₁₀ monoolefins.

The product produced via the acid catalyzed addition of H₂S to thefeedstock comprising branched C₁₀ monoolefins was prepared in acontinuous flow reactor over Filtrol® 24 acid catalyst. The reactorcontained 43.22 g of catalyst and the WHSV (weight hourly spacevelocity) was maintained at 1.0 grams of olefin per gram of catalyst perhour. The H₂S to olefin molar ratio ranged from 10:1 to 1:1. Thereaction temperature was between 120° C. to 220° C., and the reactorpressure was 450-460 psig (3,100 kPag-3,200 kPag). Optimum results,based on conversion and maximum C₁₀ mercaptan, were in the 180-200° C.range and an H₂S to olefin molar ratio of 5:1. A decrease in the H₂S toolefin ratio resulted in a decrease in the C₁₀ mercaptan fraction and acorresponding increase in the sulfide fraction. The run data for theacid catalyzed reactions are shown in Table 5.

TABLE 5 Sample # 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Mid Temp 123 145167 186 202 221 184 185 202 165 182 201 182 182 Actual Btm Temp Set 122142 162 182 202 222 185 185 205 165 185 205 185 185 Btm Temp 120 141 160179 198 219 182 182 201 163 181 201 181 182 Actual Average Actual 121142 163 182 200 221 183 184 202 163 182 202 182 182 Temp GC Analysisarea % Lights 4.34 4.24 4.16 3.95 4.24 5.85 3.85 3.88 4.08 3.97 4.043.99 4.02 3.94 Olefin Region 58.03 39.66 18.56 11.93 12.70 22.22 9.669.79 11.35 12.90 13.45 17.34 19.75 15.86 Octyl SH 0.03 0.57 1.24 0.011.67 1.48 1.19 1.19 1.44 1.06 1.12 1.06 0.83 0.92 Other Lights 0.51 0.180.13 0.00 0.73 1.26 0.40 0.33 0.54 0.00 0.01 0.02 0.24 0.21 C₁₀Mercaptan 15.64 36.81 52.84 61.44 56.82 49.41 56.57 57.48 55.80 61.9758.38 50.79 42.78 48.51 Region Intermediate 7.80 11.67 11.07 6.78 6.246.71 6.32 6.27 6.88 6.86 7.05 6.67 6.65 6.57 Heavies Sulfides 13.65 6.8812.00 15.88 17.59 13.08 22.01 21.06 19.91 13.24 15.95 20.13 25.73 24.00Raman Olefin 31.0% 56.2% 81.5% 91.0% 92.5% 89.8% 93.2% 92.2% 91.9% 86.4%85.4% 81.7% 76.2% 78.4% Conversion mol %

The best olefin conversions were in the 88-92 area % range. The C₁₀mercaptan fraction accounted for 50-60 area % of the crude productweight, while the sulfide fraction ranged from 15-25 area % of the crudeproduct weight.

Acid catalysis produced the Markovnikov product. The vinyl components ofthe feedstock comprising branched C₁₀ monoolefins produced secondarymercaptans. The internal olefin components produced secondarymercaptans, while the vinylidene components produced tertiarymercaptans. Thus, the composition of the C₁₀ mercaptan fraction isomerswas different when compared to the composition of the product obtainedby UV-initiation. For example, the 5-methyl-1-nonene isomer produced5-methyl-2-mercapto-nonane by acid catalysis; and5-methyl-1-mercapto-nonane was the major product produced byUV-initiation, with a minor amount of the 2-mercapto isomer as aby-product. The 2-butyl-1-hexene isomer produced5-methyl-5-mercapto-nonane by acid catalysis; while UV-initiationproduced 2-butyl-1-mercapto-hexane. Comparative GC traces of the productproduced by acid catalysis and that produced by UV-initiation are shownin FIG. 6 and FIG. 7. FIG. 6 shows a comparison of crude product (e.g.,only H₂S removed) by UV-initiation and acid catalysis routes, and FIG. 7compares the C₁₀ mercaptan fraction produced by the UV-initiation andacid catalysis routes.

The comparative GC traces in FIG. 6 and FIG. 7 demonstrate thatdifferent isomer distributions can be obtained depending on how thereaction of the feedstock comprising branched C₁₀ monoolefins and H₂S isinitiated. One would expect that the tertiary and secondary mercaptanswould elute more quickly than primary mercaptans. One would alsoanticipate that more branching and proximity of the branching to themercaptan would also cause those isomers to elute more quickly. The peakat 6.01 minutes was clearly n-decyl mercaptan and was expected to be thelast of the C₁₀ mercaptans to elute in this fraction.

As with the product produced by UV-initiation, the product obtained byacid catalysis consisted of three general fractions as produced as akettle product after removal of the unwanted lights fraction. The C₁₀mercaptan fraction comprised from 50-100 area % of the crude kettlecomposition. The mercaptan functionality of the C₁₀ fraction was 85-95area % secondary mercaptan and the remainder tertiary mercaptan. Theseisomers eluted in the 3.1-6.5 minute range under the utilized GCconditions.

The intermediate fraction consisted of those mercaptan peaks in the6.5-14 minute range. However, the functionality of the mercaptans wassecondary and tertiary C₁₂ to C₁₈ mercaptans. The intermediate fractioncomprised 5-15 area % of the total kettle composition.

The sulfide fraction comprised 0-70 area % of the composition of thekettle product, depending on the specific reaction conditions. Thefraction consisted of sulfides primarily of formula C₁₀H₂₁—S—C₁₀H₂₁.However, the isomer identity was different than that for the productproduced by UV-initiation. The acid produced sulfide product was basedon secondary and tertiary mercaptans rather than predominately primarymercaptans as in the UV-initiated produced product.

Example 3

HDS Catalysis produced mercaptans that were primarily similar indistribution to those produced by acid catalysis, which is theMarkovnikov distribution. However, there was a tendency to also producesome of the anti-Markovnikov distribution depending on the specificconditions utilized in the reaction step. Thus the product produced bythe HDS catalyst appeared to be a blend of product produced primarilyvia acid catalysis with some of the components of the UV-initiatedreaction.

The HDS reaction conditions were as follows: WHSV was varied from 0.75to 2 grams of olefin per gram of catalyst per hour; the molar ratio ofH₂S per olefin was varied from 2:1 to 10:1; the average reactiontemperature was 180° C. to 220° C. The catalyst used was cobaltmolybdenum on alumina, examples being to Haldor Topsoe TK-554, TK-570,or similar. Olefin conversion, as determined by Raman spectroscopy, wasin the 88-97 mol % range. The HDS test runs were performed using thefeedstock comprising branched C₁₀ monoolefins comparable to thecomposition as outlined in Table 1 are shown in Table 6 and Table 7.

TABLE 6 Sample # 19 20 21 22 23 24 25 26 27 Ratio 10 10 10 10 10 5 2 5 5H₂S/Olefin Olefin Rate 31.2 31 31.4 31.1 30.4 31.1 30.8 31.2 31.4 (g/hr)H₂S Rate 74.8 74.2 74.7 75 74.2 36.9 14.4 36.8 37 (g/hr) WHSV 0.75 0.750.75 0.75 0.75 0.75 0.75 0.75 0.75 Average 204 205 204 223 202 203 203203 203 Actual Temp GC Analysis area % Lights 6.97 5.33 5.16 4.02 4.974.98 4.77 4.59 4.83 Olefin 6.22 7.06 8.93 9.89 8.50 7.35 6.53 7.01 7.28Region Octyl SH 1.01 1.60 2.07 1.71 1.75 2.07 2.05 2.04 2.16 C₁₀ 51.4360.92 75.05 59.89 73.44 80.77 79.73 78.53 80.92 Mercaptan RegionIntermediate 3.71 4.03 3.86 4.73 4.02 3.78 3.79 4.59 3.97 heaviesSulfides 30.62 21.05 4.93 19.74 7.32 1.06 3.13 3.24 0.83 Raman 96.8%96.9% 96.1% 94.2% 96.6% 97.5% 97.9% 97.7% 97.2% Olefin Conv. mol %Notes: About 3-4% of olefin region is saturates; lights are primarilycyclohexane, octane, and ethylbenzene

TABLE 7 Sample # 28 29 30 31 32 33 34 35 36 37 38 39 Ratio 5 5 2 5 5 5 55 5 5 5 5 H₂S/Olefin Olefin Rate 40.8 41.7 41.6 62.7 61.7 60.7 81.8 82.461.7 62.7 41.8 41.2 (g/hr) H₂S Rate 50.1 49.6 20 74.7 74.5 75 99.5 9974.4 74.7 49.5 50.1 (g/hr) WHSV 1 1 1 1.50 1.50 1.50 2.00 2.00 1.50 1.501.00 1.00 Average 203 203 204 203 203 212 203 218 183 183 181 191 ActualTemp GC Analysis area % Lights 4.02 4.47 4.24 4.07 4.04 3.61 3.51 3.673.40 3.68 3.45 3.65 Olefin 7.21 8.65 7.84 11.07 11.73 10.01 13.25 14.8216.38 18.94 13.61 10.49 Region Octyl SH 1.58 1.91 1.71 1.63 1.67 1.791.42 1.50 1.12 1.21 1.19 1.48 C₁₀ 66.44 77.68 77.74 73.33 73.27 63.4959.35 65.04 58.50 64.23 65.26 71.64 Mercaptan Region Intermediate 5.635.21 5.45 5.64 5.33 7.60 7.76 8.04 8.31 7.34 8.27 8.21 Heavies Sulfides15.12 2.07 3.02 4.26 3.95 13.40 14.58 6.81 12.15 4.45 8.08 4.41 Raman96.6% 96.6% 97.0% 94.9% 93.9% 94.4% 91.1% 90.4% 87.3% 87.0% 90.9% 94.9%Olefin Conv. mol %

As can be observed from Tables 6 and 7, the trends for sulfideproduction were less consistent, possibly because the continuous reactorwas run at steady state conditions for about 4-5 hours, shut down, andrestarted the next day. Further, it appeared that the initial sampleeach day was initially higher in sulfide content than anticipated andthen declined. It appears that under similar conditions of WHSV, ratioand temperature, the HDS catalyzed reaction produces more C₁₀ mercaptanfraction and less sulfide fraction than the acid catalyzed reaction. Itis expected that the results varied compared to what would be obtainedif the reactor was operated continuously at steady state conditions forseveral weeks.

A typical GC trace of reactor crude produced from the HDS catalyzedreaction of H₂S and branched C₁₀ monoolefins is shown in FIG. 8.Comparison of the C₁₀ fraction (3.5 to 6 minute retention time) of theHDS reaction product, as shown in FIG. 8, with the same reaction productfor both the acid catalyzed and UV-initiated processes as shown in FIG.6 or FIG. 7, shows that the HDS product was a blend of the acidcatalyzed and UV-initiated products.

Example 4

Purification of Crude Decyl Mercaptan. Purification was performed onsome the crude product samples to remove the lights fraction, whichconsisted of residual H₂S, cyclohexane, ethylbenzene, octane, octene,2-ethylhexanol and as much of the n-octylmercaptan as possible, i.e.,all C⁹⁻. Purification was performed in a conventional laboratorydistillation column. Removing the light fraction, especially then-octylmercaptan, can result in the loss of some C₁₀ mercaptan isomersto the overhead distillate product. It is believed that acommercial-scale operation can minimize the loss of C₁₀ mercaptans bycontrolling operating parameters including the number of distillationcolumns used, the number of theoretical trays in the column(s), the rateof reflux and take-off, and whether the distillation is done incontinuous or batch mode. These parameters can readily be determinedwith research, allowing one of reasonable skill in the art to scale upand optimize the distillation process. It is within the scope of thisdisclosure that operating a continuous mode distillation system usingtwo columns can provide satisfactory separation. For example, operatinga the first column at an overhead temperature of 80° C.-85° C. at 9 torrand a second column at about 95° C.-97° C. would provide a satisfactoryseparation.

The distillation column used in the lab was 1″×12″ packed with stainlesssteel sponge. As stated earlier, it is believed that the separation wasnot as good as desired, and significant C₁₀ mercaptan was removedoverhead, even with the initial cut. A distillation run at 9 torr and areflux to take-off ratio of 18:3 required the removal of 12.5 area % ofthe crude overhead to reach a level of <0.1 area % lights in the kettleproduct. According to the GC analysis of the crude, only 8.1 area % ofthe crude product was lights that needed to be removed overhead. Thekettle temperature was in the 100° C.-115° C. range at 9 torr. Inanother distillation batch, 8.8 area % of the crude was taken overhead,while the lights composed only 4.0 area % of the crude. In several otherbatches, nearly 20 area % of the crude was lost overhead.

For simulation of the distillation, the nearest boiling point impuritiesare the ethylbenzene, 2-ethylhexanol and n-octylmercaptan. The amount ofthese impurities that are present will determine how many theoreticaltrays are be needed, as well as the best pressure and temperatureprofile to optimize yield and keep the level of the n-octylmercaptan toas low a value as feasible.

Prophetic Example 5

Olefin Feedstock Purification. A feedstock comprising branched C₁₀monoolefins produced in a 1-hexene process can be purified (e.g.,distilled), for improved olefin reactivity and resulting mercaptanpurity. The lights up to 1-octene can be removed and the C₁₀ olefinisomers taken overhead to high purity (>98%). This high purity C₁₀monoolefin cut would then be free of the C₁₂ to C₁₈ olefins. The highpurity C₁₀ olefin can then be reacted with H₂S to produce the mercaptanproducts. The reaction conditions would be identical for the high purityC₁₀ olefin stream (e.g., second feedstock) as already indicated for thefeedstock comprising branched C₁₀ monoolefins produced in a 1-hexeneprocess used as received (e.g., first feedstock). The major differencewill be in the composition of the crude stream and product stream. Forthe second feedstock, the crude product would consist of any residualH₂S and unreacted C₁₀ olefin, the C₁₀ mercaptan isomers and theC₁₀H₂₁—S—C₁₀H₂₁ fraction. Once the lights are removed, the product willcontain the C₁₀ mercaptan isomers and the C₂₀-sulfide, but will notcontain any of the intermediate mercaptans and asymmetric sulfidecomponents, which come from reaction of C₁₀ mercaptan with the othernon-C₁₀ olefins. The mercaptan functionality for the various routes willbe the same as already indicated.

Example 6

UV-initiation reactions of NEODENE 1112 IO higher olefins were performedin a 1.5 L UV reactor equipped with a 100 watt lamp and ballast. To203.9 g of the NEODENE 1112 IO higher olefins, 650 g of H₂S was chargedafter sealing the reactor. The reaction mixture was stirred at 500-1,000RPM. The reaction temperature was controlled with a bath set at 25° C.,but the heat of reaction did reach about 40° C. The lamp operated at1.0-1.7 amps and 25-112 volts over the course of the reaction, operatingat lower amps and higher voltages as it warmed up. The reaction pressurevaried from 315-350 psig (2,172 kPag-2,413 kPag) during the actualreaction time. The reaction was typically completed in approximately 30minutes as monitored by RAMAN spectroscopy analysis but was allowed tocontinue for 90 min to ensure completion. The H₂S was vented and thereaction mixture was purged three times with nitrogen to remove excessH₂S to the extent possible. Additional H₂S removal was conducted using arotary evaporator. The conversion was measured as 98% by gaschromatography (GC) with the constituent components determined to be 41wt. % C₁₁ mercaptan, 41 wt. % C₁₂ mercaptan, ˜4 wt. % sulfides and 14wt. % unreacted olefin. Distillation of the C₁₁₊ mercaptans crudecomposition sample was performed at a kettle temperature of 137° C. andwas complete when the head temperature reached ˜120° C. at 9 mm Hgvacuum to give a kettle product with low perceived odor. The productmixture or kettle product (containing the intermediate and heavyfractions recovered from the C₁₁₊ mercaptans crude composition) wasanalyzed by GC and determined to be 40.2 wt. % C₁₁ mercaptan, 53 wt. %C₁₂ mercaptan, 7 wt. % sulfides and 0.3 wt. % light mercaptan/unreactedolefin. Mercaptan sulfur was determined using titration as well anddetermined to be 16 wt. % vs. a GC calculation of 15.4 wt. %. Totalsulfur was determined by X-ray to be 16.8 wt. % versus a GC calculationof ˜15.8 wt. %.

Example 7

UV-initiation reactions of NEODENE 1314 IO higher olefins were performedin a 1.5 L UV reactor equipped with a 100 watt lamp and ballast. The UVprepared sample was prepared in the 1.5 L UV reactor equipped with a 100watt lamp and ballast. To 229.6 g of the NEODENE 1314 IO higher olefins,650 g of H₂S was charged after sealing the reactor. The reaction mixturewas stirred at 500-1,000 RPM. The reaction temperature was controlledwith a bath set at 25° C., but the heat of reaction did reach about 40°C. The lamp operated at 1.0-1.5 amps and 25-110 volts over the course ofthe reaction, operating at lower amps and higher voltages as it warmedup. The reaction pressure varied from 305-340 psig (2,103 kPag-2,344kPag) during the actual reaction time. The reaction was typicallycompleted in approximately 30 minutes as monitored by RAMAN spectroscopyanalysis but was allowed to continue for 70 min to ensure completion.The H₂S was vented and the reaction mixture purged three times withnitrogen to remove excess H₂S to the extent possible. Additional H₂Sremoval was conducted using a rotary evaporator. The conversion wasmeasured as 79% by GC with the constituent components determined to be38 wt. % C₁₃ mercaptan, 39.4 wt. % C₁₄ mercaptan, ˜2 wt. % sulfides and21 wt. % unreacted olefin. Distillation of the C₁₁₊ mercaptans crudecomposition sample was performed at a kettle temperature of 149° C. andwas complete when the head temperature reached ˜100° C. at 3 mm Hgvacuum to give a kettle product with low perceived odor. The productmixture or kettle product (containing the intermediate and heavyfractions recovered from the C₁₁₊ mercaptans crude composition) wasanalyzed by GC and determined to be 45 wt. % C₁₃ mercaptan, 46 wt. % C₁₄mercaptan, 6 wt. % sulfides and 3 wt. % light mercaptan/unreactedolefin. Mercaptan sulfur was determined using titration as well anddetermined to be 14 wt. % vs. a GC calculation of 13.1 wt. %. Totalsulfur was determined by X-ray to be 14.6 wt. % versus a GC calculationof ˜13.5 wt. %.

Example 8

UV-initiation reactions of NEODENE 14/16 higher olefins were performedin a 1.5 L UV reactor equipped with a 100 watt lamp and ballast. To217.6 g of the NEODENE 14/16 higher olefins, 650 g of H₂S was chargedafter sealing the reactor. The reaction mixture was stirred at 500-1,000RPM. The reaction temperature was controlled with a bath set at 25° C.,but the heat of reaction did reach about 40° C. The lamp operated at1.0-1.6 amps and 25-120 volts over the course of the reaction, operatingat lower amps and higher voltages as it warmed up. The reaction pressurevaried from 310-340 psig (2,137 kPag-2,344 kPag) during the actualreaction time. The reaction was typically completed in approximately 30minutes as monitored by RAMAN analysis but was allowed to continue for55 min to ensure completion. The H₂S was vented and the reaction mixturepurged three times with nitrogen to remove excess H₂S to the extentpossible. Additional H₂S removal was conducted using a rotaryevaporator. The conversion was measured as 93% by GC with theconstituent components determined to be 57.4 wt. % C₁₄ mercaptan, 30.1wt. % C₁₆ mercaptan, ˜6 wt. % sulfides and 7 wt. % unreacted olefin.Distillation of the C₁₁₊ mercaptans crude composition sample wasperformed at a kettle temperature of 170° C. and was complete when thehead temperature reached ˜40° C. at 0 mm Hg vacuum to give a kettleproduct with low perceived odor. The product mixture or kettle product(containing the intermediate and heavy fractions recovered from the C₁₁₊mercaptans crude composition) was analyzed by GC and determined to be 57wt. % C₁₄ mercaptan, 30 wt. % C₁₆ mercaptan, 13.4 wt. % sulfides and 0wt. % light mercaptan/unreacted olefin. Mercaptan sulfur was determinedusing titration as well and determined to be 12 wt. % vs. a GCcalculation of 11.6 wt. %. Total sulfur was determined by X-ray to be12.9 wt. % versus a GC calculation of ˜12.5 wt. %.

ADDITIONAL DISCLOSURE

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the detailed description of the present invention.The disclosures of all patents, patent applications, and publicationscited herein are hereby incorporated by reference.

A first embodiment, which is a composition comprising mercaptans,wherein at least about 50 wt. % of the mercaptans are branched C₁₀mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

A second embodiment, which is a composition comprising sulfides, whereinat least about 50 wt. % of the sulfides are branched C₂₀ sulfidesrepresented by the structure R¹—S—R² wherein R¹ and R² are eachindependently a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

A third embodiment, which is the composition of the second embodiment,wherein the olefin comprises a) at least 76 mol % C₁₀ monoolefins, theC₁₀ monoolefins comprising i) at least 3 mol % 2-butyl-1-hexene(represented by Structure L), ii) at least 8 mol % 3-propyl-1-heptene(represented by Structure J), iii) at least 6 mol % 4-ethyl-1-octene(represented by Structure K), and iv) at least 20 mol %5-methyl-1-nonene (represented by Structure I); and b) at least 1 mol %C₁₄ monoolefins.

A fourth embodiment, which is the composition of the third embodiment,wherein the C₁₀ monoolefins comprise from 1 mol % to 16 mol % 4-deceneand/or 5-decene.

A fifth embodiment, which is the composition of any one of the thirdthrough the fourth embodiments, wherein the C₁₀ monoolefins comprisefrom 0.5 mol % to 9 mol % 1-decene.

A sixth embodiment, which is the composition of any one of the secondthrough the fifth embodiments, wherein the olefin further comprises from0.1 mol % to 5 mol % C₁₂ monoolefins, the C₁₂ monoolefins comprisingfrom 54 mol % to 74 mol % 1-dodecene.

A seventh embodiment, which is the composition of any one of the secondthrough the sixth embodiments, wherein the olefin further comprises from0.1 mol % to 5 mol % C₈ monoolefins, the C₈ monoolefins comprising atleast 95 mol % 1-octene.

An eighth embodiment, which is the composition of any one of the firstthrough the seventh embodiments, wherein the olefin further comprisesfrom 0.05 mol % to 2 mol % C₁₆ monoolefins and/or C₁₈ monoolefins.

A ninth embodiment, which is a composition comprising:

(A) at least about 25 wt. % C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and

(B) at least about 5 wt. % C₂₀ sulfides represented by the structureR¹—S—R², wherein R¹ and R² are each independently a functional groupderived from an olefin, wherein the olefin comprises 5-methyl-1-nonene(represented by Structure I), 3-propyl-1-heptene (represented byStructure J), 4-ethyl-1-octene (represented by Structure K),2-butyl-1-hexene (represented by Structure L), or combinations thereof.

A tenth embodiment, which is a composition comprising:

(A) from at least about 50 wt. % to at least about 90 wt. % mercaptans,wherein at least about 50 wt. % of the mercaptans are branched C₁₀mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and

(B) from at least about 10 wt. % to at least about 30 wt. % sulfides,wherein at least 50 wt. % of the sulfides are branched C₂₀ sulfidesrepresented by the structure R¹—S—R², wherein R¹ and R² are eachindependently a functional group derived from an olefin selected fromthe group consisting of 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), and combinations thereof.

An eleventh embodiment, which is a composition comprising:

(A) at least about 25 wt. % C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof;

(B) at least about 5 wt. % C₂₀ sulfides represented by the structureR¹—S—R², wherein R¹ and R² are each independently a functional groupderived from an olefin, wherein the olefin comprises 5-methyl-1-nonene(represented by Structure I), 3-propyl-1-heptene (represented byStructure J), 4-ethyl-1-octene (represented by Structure K),2-butyl-1-hexene (represented by Structure L), or combinations thereof;and one or more of the following components (C)-(I):

(C) less than about 5 wt. % C₈ mercaptans;

(D) less than about 15 wt. % C₁₂ mercaptans;

(E) less than about 15 wt. % C₁₄ mercaptans;

(F) less than about 5 wt. % C₁₆ mercaptans and/or C₁₈ mercaptans;

(G) less than about 1 wt. % C₁₆₋₃₆ sulfides represented by the structureR³—S—R⁴, wherein R³ and R⁴ are each independently a functional groupderived from an olefin selected from the group consisting of C₈monoolefins, C₁₀ monoolefins, C₁₂ monoolefins, C₁₄ monoolefins, C₁₆monoolefins, and C₁₈ monoolefins, wherein R³ and R⁴ are not bothbranched C₁₀ monoolefins;

(H) less than about 10 wt. % unreacted C₈₋₁₈ monoolefins; and

(I) less than about 10 wt. % non-olefin impurities selected from thegroup consisting of C₈₋₁₄ alkanes, cyclohexane, methylcyclopentane,methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene,hexamethylbenzene, C₄₋₁₂ alcohols, 2-ethyl-1-hexanol, and2-ethylhexyl-2-ethylhexanoate.

A twelfth embodiment, which is a process comprising reacting hydrogensulfide (H₂S) and a feedstock comprising one or more branched C₁₀monoolefins in the presence of an initiating agent to produce a crudecomposition, wherein the branched C₁₀ monoolefins comprise5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

A thirteenth embodiment, which is the process of the twelfth embodimentfurther comprising recovering a first reaction product from the crudecomposition, wherein the first reaction product comprises at least about25 wt. % branched C₁₀ mercaptans.

A fourteenth embodiment, which is the process of any one of the twelfththrough the thirteenth embodiments further comprising recovering asecond reaction product from the crude composition, wherein the secondreaction product comprises at least about 5 wt. % branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein R¹ and R² are eachindependently a branched C₁₀ alkyl group derived from the branched C₁₀monoolefin, and wherein the branched C₁₀ alkyl group is selected fromthe group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ sulfide.

A fifteenth embodiment, which is the process of any one of the twelfththrough the fourteenth embodiments further comprising recovering areaction product from the crude composition, wherein the reactionproduct comprises (i) at least about 50 wt. % mercaptans, wherein atleast about 50 wt. % of the mercaptans are branched C₁₀ mercaptansselected from the group consisting of 5-methyl-1-mercapto-nonane(represented by Structure A), 3-propyl-1-mercapto-heptane (representedby Structure B), 4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (ii) at least about 10 wt. % sulfides, whereinat least about 50 wt. % of the sulfides are branched C₂₀ sulfidesrepresented by the structure R¹—S—R², wherein R¹ and R² are eachindependently a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

A sixteenth embodiment, which is the process of any one of the twelfththrough the fifteenth embodiments, wherein the initiating agentcomprises ultraviolet radiation.

A seventeenth embodiment, which is the process of the sixteenthembodiment, wherein the initiating agent further comprises a phosphitepromoter, a photoinitiator, or both.

An eighteenth embodiment, which is the process of any one of the twelfththrough the seventeenth embodiments, wherein the initiating agentcomprises an acid catalyst.

A nineteenth embodiment, which is the process of any one of the twelfththrough the eighteenth embodiments, wherein the initiating agentcomprises a hydrodesulfurization catalyst.

A twentieth embodiment, which is the process of the sixteenthembodiment, wherein the crude composition comprises C₁₀ mercaptanscomprising from about 70 wt. % to about 95 wt. % C₁₀ primary mercaptans,from about 10 wt. % to about 20 wt. % C₁₀ secondary mercaptans, and fromabout 0 wt. % to about 5 wt. % C₁₀ tertiary mercaptans.

A twenty-first embodiment, which is the process of the eighteenthembodiment, wherein the crude composition comprises C₁₀ mercaptanscomprising from about 0 wt. % to about 5 wt. % C₁₀ primary mercaptans,from about 80 wt. % to about 95 wt. % C₁₀ secondary mercaptans, and fromabout 5 wt. % to about 20 wt. % C₁₀ tertiary mercaptans.

A twenty-second embodiment, which is the process of the nineteenthembodiment, wherein the crude composition comprises C₁₀ mercaptanscomprising from about 5 wt. % to about 30 wt. % C₁₀ primary mercaptans,from about 60 wt. % to about 75 wt. % C₁₀ secondary mercaptans, and fromabout 5 wt. % to about 15 wt. % C₁₀ tertiary mercaptans.

A twenty-third embodiment, which is the process of any one of thetwelfth through the twenty-second embodiments further comprising, priorto the reacting, separating the feedstock comprising one or morebranched C₁₀ monoolefins from an effluent stream obtained from a1-hexene production process.

A twenty-fourth embodiment, which is the product made by the process ofany one of the twelfth through the twenty-third embodiments.

A first aspect, which is a process comprising reacting hydrogen sulfide(H₂S) and a feedstock comprising one or more C₁₁₊ monoolefins in thepresence of an initiating agent to produce a C₁₁₊ mercaptans crudecomposition, wherein the feedstock comprises at least about 70 wt. % ofone or more C₁₁₊ monoolefins, based on the total weight of thefeedstock, and wherein the C₁₁₊ monoolefins comprise C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; C₁₄ and C₁₆linear alpha monoolefins; or combinations thereof.

A second aspect, which is the process of the first aspect, wherein thefeedstock comprises (A) at least about 30 wt. % C₁₁ internalmonoolefins, and (B) at least about 40 wt. % C₁₂ internal monoolefins;based on the total weight of the feedstock.

A third aspect, which is the process of the first aspect, wherein thefeedstock comprises (A) at least about 35 wt. % C₁₃ internalmonoolefins, and (B) at least about 35 wt. % C₁₄ internal monoolefins;based on the total weight of the feedstock.

A fourth aspect, which is the process of the first aspect, wherein thefeedstock comprises (A) at least about 50 wt. % 1-tetradecene, and (B)at least about 20 wt. % 1-hexadecene; based on the total weight of thefeedstock.

A fifth aspect, which is the process of any one of the first through thefourth aspects, wherein the C₁₁₊ mercaptans crude composition comprisesless than about 10 wt. %, C₂₂₊ sulfides, based on the total weight ofthe crude composition, wherein the C₂₂₊ sulfides are characterized bystructure R⁷—S—R⁸, wherein both R⁷ and R⁸ are each independently analkyl group derived from the one or more C₁₁₊ monoolefins, and whereinthe C₁₁₊ monoolefins comprise C₁₁ internal monoolefins, C₁₂ internalmonoolefins, C₁₃ internal monoolefins, C₁₄ internal monoolefins,1-tetradecene, 1-hexadecene, or combinations thereof.

A sixth aspect, which is the process of any one of the first through thefifth aspects further comprising recovering a reaction product from theC₁₁₊ mercaptans crude composition, wherein the reaction productcomprises at least about 50 wt. % C₁₁₊ mercaptans, based on the totalweight of the reaction product, wherein the C₁₁₊ mercaptans arecharacterized by structure R⁶—SH, wherein R⁶ is an alkyl group derivedfrom the one or more C₁₁₊ monoolefins, and wherein the C₁₁₊ monoolefinscomprise C₁₁ internal monoolefins, C₁₂ internal monoolefins, C₁₃internal monoolefins, C₁₄ internal monoolefins, 1-tetradecene,1-hexadecene, or combinations thereof.

A seventh aspect, which is the process of the sixth aspect, wherein thereaction product further comprises less than about 20 wt. %, C₂₂₊sulfides, based on the total weight of the reaction product, wherein theC₂₂₊ sulfides are characterized by structure R⁷—S—R⁸, wherein both R⁷and R⁸ are each independently an alkyl group derived from the one ormore C₁₁₊ monoolefins, and wherein the C₁₁₊ monoolefins comprise C₁₁internal monoolefins, C₁₂ internal monoolefins, C₁₃ internalmonoolefins, C₁₄ internal monoolefins, 1-tetradecene, 1-hexadecene, orcombinations thereof.

An eighth aspect, which is the process of the seventh aspect, whereinthe initiating agent comprises ultraviolet radiation.

A ninth aspect, which is the process of the eighth aspect, wherein theinitiating agent further comprises a phosphite promoter, aphotoinitiator, a sulfur scavenger, an antioxidant, or combinationsthereof.

A tenth aspect, which is the process of the ninth aspect, wherein theinitiating agent further comprises the phosphite promoter, wherein thephosphite promoter is used in an amount of from about 0.01 wt. % toabout 5 wt. % based on a total weight of olefins in the feedstock.

A eleventh aspect, which is the process of the tenth aspect, wherein thephosphite promoter is characterized by formula P(OR⁵)₃, wherein each R⁵can independently be a C₁-C₁₈ hydrocarbyl group.

A twelfth aspect, which is the process of the eleventh aspect, whereineach R⁵ can be a methyl group, an ethyl group, a propyl group, a butylgroup, a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, a decyl group; a phenyl group, a tolyl group, a xylylgroup, or a naphthyl group.

A thirteenth aspect, which is the process of any one of the firstthrough the twelfth aspects, wherein the initiating agent furthercomprises the photoinitiator, wherein the photoinitiator is used in anamount of from about 0.05 wt. % to about 5 wt. % based on a total weightof olefins in the feedstock.

A fourteenth aspect, which is the process of the thirteenth aspect,wherein the photoinitiator comprises 1-hydroxy-cyclohexyl-phenyl-ketone,benzophenone, Bis-(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methy-1-propan-1-one,2-hydroxy-2-methyl-1-phenyl-1-propanone, or combinations thereof.

A fifteenth aspect, which is the process of any one of the first throughthe fourteenth aspects, wherein the initiating agent comprises an acidcatalyst.

A sixteenth aspect, which is the process of the fifteenth aspect,wherein the acid catalyst comprises an acid washed clay; an acid washedbentonite; a tetrafluoroethylene polymer resin modified withperfluorovinyl ether groups terminated with sulfonate groups; amacroreticular, sulfonated, crosslinked copolymer of styrene and divinylbenzene; or combinations thereof.

A seventeenth aspect, which is the process of any one of the firstthrough the sixteenth aspects, wherein the initiating agent comprises ahydrodesulfurization catalyst.

An eighteenth aspect, which is the process of any one of the firstthrough the seventeenth aspects, wherein the reacting occurs at atemperature of from about 0° C. to about 300° C. and at a H₂S to C₁₁₊monoolefins molar ratio of from about 1:1 to about 15:1.

A nineteenth aspect, which is the product made by the process of any oneof the first through the eighteenth aspects.

A twentieth aspect, which is a process comprising reacting hydrogensulfide (H₂S) and a feedstock comprising one or more C₁₁₊ monoolefins inthe presence of an initiating agent to produce a C₁₁₊ mercaptans crudecomposition, wherein the feedstock comprises at least about 70 wt. % ofone or more C₁₁₊ monoolefins, based on the total weight of thefeedstock, and wherein the C₁₁₊ monoolefins comprise C₁₁ internalmonoolefins, C₁₂ internal monoolefins, C₁₃ internal monoolefins, C₁₄internal monoolefins, 1-tetradecene, 1-hexadecene, or combinationsthereof; and recovering a reaction product from the C₁₁₊ mercaptanscrude composition, wherein the reaction product comprises (A) at leastabout 50 wt. % C₁₁₊ mercaptans, based on the total weight of thereaction product, wherein the C₁₁₊ mercaptans are characterized bystructure R⁶ SH, wherein R⁶ is an alkyl group derived from the one ormore C₁₁₊ monoolefins; and (B) less than about 20 wt. %, C₂₂₊ sulfides,based on the total weight of the reaction product, wherein the C₂₂₊sulfides are characterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸are each independently an alkyl group derived from the one or more C₁₁₊monoolefins.

A twenty-first aspect, which is a composition comprising at least about50 wt. % C₁₁₊ mercaptans, based on the total weight of the composition,wherein the C₁₁₊ mercaptans are characterized by structure R⁶—SH,wherein R⁶ is an alkyl group derived from one or more C₁₊ monoolefins,and wherein the one or more C₁₁₊ monoolefins comprise C₁₁ internalmonoolefins, C₁₂ internal monoolefins, C₁₃ internal monoolefins, C₁₄internal monoolefins, 1-tetradecene, 1-hexadecene, or combinationsthereof.

A twenty-second aspect, which is a composition comprising C₂₂₊ sulfides,wherein at least about 50 wt. % of the C₂₂₊ sulfides are C₂₂₊ sulfidescharacterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸ are eachindependently an alkyl group derived from one or more C₁₁₊ monoolefins,and wherein the one or more C₁₁₊ monoolefins comprise C₁₁ internalmonoolefins, C₁₂ internal monoolefins, C₁₃ internal monoolefins, C₁₄internal monoolefins, 1-tetradecene, 1-hexadecene, or combinationsthereof.

A twenty-third aspect, which is a composition comprising (A) at leastabout 50 wt. % C₁₁₊ mercaptans, based on the total weight of thecomposition, wherein the C₁₁₊ mercaptans are characterized by structureR⁶—SH, wherein R⁶ is an alkyl group derived from one or more C₁₁₊monoolefins, wherein the one or more C₁₁₊ monoolefins comprise C₁₁internal monoolefins, C₁₂ internal monoolefins, C₁₃ internalmonoolefins, C₁₄ internal monoolefins, 1-tetradecene, 1-hexadecene, orcombinations thereof; and (B) at least about 1 wt. % C₂₂₊ sulfides,wherein at least about 50 wt. % of the C₂₂ sulfides are C₂₂ sulfidescharacterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸ are eachindependently an alkyl group derived from the one or more C₁₁monoolefins.

A twenty-fourth aspect, which is a composition comprising (A) from atleast about 50 wt. % to at least about 99 wt. % C₁₁₊ mercaptans, basedon the total weight of the composition, wherein at least about 50 wt. %of the C₁₁ mercaptans are C₁₁₊ mercaptans characterized by structureR⁶—SH, wherein R⁶ is an alkyl group derived from one or more C₁₁monoolefins, wherein the one or more C₁₁₊ monoolefins comprise C₁₁internal monoolefins, C₁₂ internal monoolefins, C₁₃ internalmonoolefins, C₁₄ internal monoolefins, 1-tetradecene, 1-hexadecene, orcombinations thereof; and (B) from at least about 1 wt. % to at leastabout 20 wt. % C₂₂₊ sulfides, wherein at least about 50 wt. % of theC₂₂₊ sulfides are C₂₂₊ sulfides characterized by structure R⁷—S—R⁸,wherein both R⁷ and R⁸ are each independently an alkyl group derivedfrom the one or more C₁₁₊ monoolefins.

A twenty-fifth aspect, which is a composition comprising C₁₀₊mercaptans, wherein at least about 50 wt. % of the C₁₀₊ mercaptans arebranched C₁₀ to C₃₀ mercaptans characterized by the general formulaR¹⁴—SH, wherein R¹⁴ is a branched alkyl group; and wherein R¹⁴ has from10 to 30 carbon atoms.

A twenty-sixth aspect, which is the composition of the twenty-fifthaspect, wherein the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH are selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and wherein R⁹is a C₁ to C₂₁ alkyl group.

A twenty-seventh aspect, which is the composition of any one of thetwenty-fifth and the twenty-sixth aspect, wherein R⁹ is a C₂ to C₂₁alkyl group.

A twenty-eighth aspect, which is a composition comprising C₂₀₊ sulfides,wherein at least about 50 wt. % of the C₂₀₊ sulfides are branched C₂₀ toC₆₀ sulfides represented by structure R¹⁰—S—R¹¹, wherein R¹⁰ and R¹¹ areeach independently a functional group derived from an olefin, andwherein the olefin comprises a branched C₁₀ to C₃₀ monoolefin.

A twenty-ninth aspect, which is the composition of the twenty-eighthaspect, wherein the branched C₁₀ to C₃₀ monoolefin comprises a branchedC₁₀ to C₃₀ monoolefin represented by Structure I-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof; andwherein R⁹ is a C₁ to C₂₁ alkyl group.

A thirtieth aspect, which is the composition of the twenty-ninth aspect,wherein R⁹ is a C₂ to C₂₁ alkyl group.

A thirty-first aspect, which is the composition of any one of thetwenty-eighth through the thirtieth aspects, wherein the olefin furthercomprises from about 0.1 mol % to about 26 mol % linear C₁₀ to C₃₀monoolefins.

A thirty-second aspect, which is the composition of any one of thetwenty-eighth through the thirty-first aspects, wherein the olefinfurther comprises from about 0.1 mol % to about 5 mol % C₈ monoolefins,the C₈ monoolefins comprising at least about 95 mol % 1-octene.

A thirty-third aspect, which is the composition of any one of thetwenty-eighth through the thirty-second aspects, wherein the olefincomprises i) at least about 70 wt. % branched C₁₀ to C₃₀ monoolefins;ii) less than about 15 wt. % C⁹⁻ monoolefins; and iii) less than about15 wt. % C₃₁₊ monoolefins; based on the total weight of the olefin.

A thirty-fourth aspect, which is a composition comprising (A) at leastabout 25 wt. % branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group; andwherein R¹⁴ has from 10 to 30 carbon atoms; and (B) at least about 5 wt.% branched C₂₀ to C₆₀ sulfides represented by structure R¹⁰—S—R¹¹,wherein R¹⁰ and R¹¹ are each independently a functional group derivedfrom an olefin, and wherein the olefin comprises a branched C₁₀ to C₃₀monoolefin.

A thirty-fifth aspect, which is the composition of the thirty-fourthaspect, wherein the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH are selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein thebranched C₁₀ to C₃₀ monoolefin comprises a branched C₁₀ to C₃₀monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof; andwherein R⁹ is a C₁ to C₂₁ alkyl group.

A thirty-sixth aspect, which is the composition of the thirty-fifthaspect, wherein R⁹ is a C₂ to C₂₁ alkyl group.

A thirty-seventh aspect, which is a process comprising reacting hydrogensulfide (H₂S) and a feedstock comprising one or more branched C₁₀ to C₃₀monoolefins in the presence of an initiating agent to produce a branchedC₁₀₊ mercaptans crude composition, wherein the branched C₁₀₊ mercaptanscrude composition comprises branched C₁₀ to C₃₀ mercaptans characterizedby the general formula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group;and wherein R¹⁴ has from 10 to 30 carbon atoms.

A thirty-eighth aspect, which is the process of the thirty-seventhaspect further comprising recovering a first reaction product from thebranched C₁₀₊ mercaptans crude composition, wherein the first reactionproduct comprises at least about 25 wt. % branched C₁₀ to C₃₀mercaptans.

A thirty-ninth aspect, which is the process of any one of thethirty-seventh and the thirty-eighth aspects further comprisingrecovering a second reaction product from the branched C₁₀₊ mercaptanscrude composition, wherein the second reaction product comprises atleast about 5 wt. % branched C₂₀ to C₆₀ sulfides represented bystructure R¹⁰—S—R¹¹, wherein R¹⁰ and R¹¹ are each independently abranched C₁₀ to C₃₀ alkyl group derived from a branched C₁₀ to C₃₀monoolefin.

A fortieth aspect, which is the process of the thirty-ninth aspect,wherein the branched C₁₀ to C₃₀ alkyl group is selected from the groupconsisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ to C₆₀ sulfide; andwherein R⁹ is a C₁ to C₂₁ alkyl group.

A forty-first aspect, which is the process of any one of thethirty-seventh through the fortieth aspects, wherein the initiatingagent comprises ultraviolet radiation.

A forty-second aspect, which is the process of the forty-first aspect,wherein the initiating agent further comprises a phosphite promoter, aphotoinitiator, a sulfur scavenger, an antioxidant, or combinationsthereof.

A forty-third aspect, which is the process of any one of thethirty-seventh through the forty-second aspects, wherein the branchedC₁₀₊ mercaptans crude composition comprises C₁₀ to C₃₀ mercaptanscomprising from about 70 wt. % to about 95 wt. % C₁₀ to C₃₀ primarymercaptans, from about 10 wt. % to about 20 wt. % C₁₀ to C₃₀ secondarymercaptans, and from about 0 wt. % to about 5 wt. % C₁₀ to C₃₀ tertiarymercaptans.

A forty-fourth aspect, which is the process of any one of thethirty-seventh through the fortieth aspects, wherein the initiatingagent comprises an acid catalyst.

A forty-fifth aspect, which is the process of the forty-fourth aspect,wherein the branched C₁₀₊ mercaptans crude composition comprises C₁₀ toC₃₀ mercaptans comprising from about 0 wt. % to about 5 wt. % C₁₀ to C₃₀primary mercaptans, from about 80 wt. % to about 95 wt. % C₁₀ to C₃₀secondary mercaptans, and from about 5 wt. % to about 20 wt. % C₁₀ toC₃₀ tertiary mercaptans.

A forty-sixth aspect, which is the process of any one of thethirty-seventh through the fortieth aspects, wherein the initiatingagent comprises a hydrodesulfurization catalyst.

A forty-seventh aspect, which is the process of the forty-sixth aspect,wherein the branched C₁₀₊ mercaptans crude composition comprises C₁₀ toC₃₀ mercaptans comprising from about 5 wt. % to about 30 wt. % C₁₀ toC₃₀ primary mercaptans, from about 60 wt. % to about 75 wt. % C₁₀ to C₃₀secondary mercaptans, and from about 5 wt. % to about 15 wt. % C₁₀ toC₃₀ tertiary mercaptans.

A forty-eighth aspect, which is a product made by the process of any oneof the thirty-seventh through the forty-seventh aspects.

While embodiments of the disclosure have been shown and described,modifications thereof can be made without departing from the spirit andteachings of the invention. The embodiments and examples describedherein are exemplary only, and are not intended to be limiting. Manyvariations and modifications of the invention disclosed herein arepossible and are within the scope of the invention.

At least one embodiment is disclosed and variations, combinations,and/or modifications of the embodiment(s) and/or features of theembodiment(s) made by a person having ordinary skill in the art arewithin the scope of the disclosure. Alternative embodiments that resultfrom combining, integrating, and/or omitting features of theembodiment(s) are also within the scope of the disclosure. Wherenumerical ranges or limitations are expressly stated, such expressranges or limitations should be understood to include iterative rangesor limitations of like magnitude falling within the expressly statedranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4,etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example,whenever a numerical range with a lower limit, R_(l), and an upperlimit, R_(u), is disclosed, any number falling within the range isspecifically disclosed. In particular, the following numbers within therange are specifically disclosed: R=R_(l)+k* (R_(u)−R_(l)), wherein k isa variable ranging from 1 percent to 100 percent with a 1 percentincrement, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5percent, . . . 50 percent, 51 percent, 52 percent . . . 95 percent, 96percent, 97 percent, 98 percent, 99 percent, or 100 percent. Moreover,any numerical range defined by two R numbers as defined in the above isalso specifically disclosed. Use of the term “optionally” with respectto any element of a claim means that the element is required, oralternatively, the element is not required, both alternatives beingwithin the scope of the claim. Use of broader terms such as comprises,includes, and having should be understood to provide support fornarrower terms such as consisting of, consisting essentially of, andcomprised substantially of.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the detailed description of the present invention.The disclosures of all patents, patent applications, and publicationscited herein are hereby incorporated by reference.

What is claimed is:
 1. A composition comprising C₁₀₊ mercaptans, whereinat least about 50 wt. % of the C₁₀₊ mercaptans are branched C₁₀ to C₃₀mercaptans characterized by the general formula R¹⁴—SH, wherein R¹⁴ is abranched alkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms. 2.The composition of claim 1, wherein the branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH are selected from the groupconsisting of a branched C₁₀ to C₃₀ mercaptan represented by StructureA-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure B-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure C-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure D-1, a branched C₁₀ to C₃₀mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and wherein R⁹is a C₁ to C₂₁ alkyl group.


3. The composition of claim 1, wherein R⁹ is a C₂ to C₂₁ alkyl group. 4.A composition comprising C₂₀₊ sulfides, wherein at least about 50 wt. %of the C₂₀₊ sulfides are branched C₂₀ to C₆₀ sulfides represented bystructure R¹⁰—S—R¹¹, wherein R¹⁰ and R¹¹ are each independently afunctional group derived from an olefin, and wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin.
 5. The composition of claim4, wherein the branched C₁₀ to C₃₀ monoolefin comprises a branched C₁₀to C₃₀ monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof; andwherein R⁹ is a C₁ to C₂₁ alkyl group.


6. The composition of claim 5, wherein R⁹ is a C₂ to C₂₁ alkyl group. 7.The composition of claim 4, wherein the olefin further comprises fromabout 0.1 mol % to about 26 mol % linear C₁₀ to C₃₀ monoolefins.
 8. Thecomposition of claim 4, wherein the olefin further comprises from about0.1 mol % to about 5 mol % C₈ monoolefins, the C₈ monoolefins comprisingat least about 95 mol % 1-octene.
 9. The composition of claim 4, whereinthe olefin comprises i) at least about 70 wt. % branched C₁₀ to C₃₀monoolefins; ii) less than about 15 wt. % C⁹⁻ monoolefins; and iii) lessthan about 15 wt. % C₃₁₊ monoolefins; based on the total weight of theolefin.
 10. A composition comprising: (A) at least about 25 wt. %branched C₁₀ to C₃₀ mercaptans characterized by the general formulaR¹⁴—SH, wherein R¹⁴ is a branched alkyl group; and wherein R¹⁴ has from10 to 30 carbon atoms; and (B) at least about 5 wt. % branched C₂₀ toC₆₀ sulfides represented by structure R¹⁰—S—R¹¹, wherein R¹⁰ and R¹¹ areeach independently a functional group derived from an olefin, andwherein the olefin comprises a branched C₁₀ to C₃₀ monoolefin.
 11. Thecomposition of claim 10, wherein the branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH are selected from the groupconsisting of a branched C₁₀ to C₃₀ mercaptan represented by StructureA-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure B-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure C-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure D-1, a branched C₁₀ to C₃₀mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein thebranched C₁₀ to C₃₀ monoolefin comprises a branched C₁₀ to C₃₀monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof; andwherein R⁹ is a C₁ to C₂₁ alkyl group.
 12. The composition of claim 11,wherein R⁹ is a C₂ to C₂₁ alkyl group.
 13. A process comprising reactinghydrogen sulfide (H₂S) and a feedstock comprising one or more branchedC₁₀ to C₃₀ monoolefins in the presence of an initiating agent to producea branched C₁₀₊ mercaptans crude composition, wherein the branched C₁₀₊mercaptans crude composition comprises branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH, wherein R¹⁴ is a branchedalkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms.
 14. Theprocess of claim 13 further comprising recovering a first reactionproduct from the branched C₁₀₊ mercaptans crude composition, wherein thefirst reaction product comprises at least about 25 wt. % branched C₁₀ toC₃₀ mercaptans.
 15. The process of claim 13 further comprisingrecovering a second reaction product from the branched C₁₀₊ mercaptanscrude composition, wherein the second reaction product comprises atleast about 5 wt. % branched C₂₀ to C₆₀ sulfides represented bystructure R¹⁰—S—R¹¹, wherein R¹⁰ and R¹¹ are each independently abranched C₁₀ to C₃₀ alkyl group derived from a branched C₁₀ to C₃₀monoolefin.
 16. The process of claim 15, wherein the branched C₁₀ to C₃₀alkyl group is selected from the group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ to C₆₀ sulfide; and wherein R⁹ is a C₁ to C₂₁ alkyl group.
 17. Theprocess of claim 13, wherein the initiating agent comprises ultravioletradiation.
 18. The process of claim 17, wherein the initiating agentfurther comprises a phosphite promoter, a photoinitiator, a sulfurscavenger, an antioxidant, or combinations thereof.
 19. The process ofclaim 17, wherein the branched C₁₀₊ mercaptans crude compositioncomprises C₁₀ to C₃₀ mercaptans comprising from about 70 wt. % to about95 wt. % C₁₀ to C₃₀ primary mercaptans, from about 10 wt. % to about 20wt. % C₁₀ to C₃₀ secondary mercaptans, and from about 0 wt. % to about 5wt. % C₁₀ to C₃₀ tertiary mercaptans.
 20. The process of claim 13,wherein the initiating agent comprises an acid catalyst.
 21. The processof claim 20, wherein the branched C₁₀₊ mercaptans crude compositioncomprises C₁₀ to C₃₀ mercaptans comprising from about 0 wt. % to about 5wt. % C₁₀ to C₃₀ primary mercaptans, from about 80 wt. % to about 95 wt.% C₁₀ to C₃₀ secondary mercaptans, and from about 5 wt. % to about 20wt. % C₁₀ to C₃₀ tertiary mercaptans.
 22. The process of claim 13,wherein the initiating agent comprises a hydrodesulfurization catalyst.23. The process of claim 22, wherein the branched C₁₀₊ mercaptans crudecomposition comprises C₁₀ to C₃₀ mercaptans comprising from about 5 wt.% to about 30 wt. % C₁₀ to C₃₀ primary mercaptans, from about 60 wt. %to about 75 wt. % C₁₀ to C₃₀ secondary mercaptans, and from about 5 wt.% to about 15 wt. % C₁₀ to C₃₀ tertiary mercaptans.
 24. A product madeby the process of claim 13.